JPS62270949A - Silver halide photographic sensitive material suppressed in generation of fog - Google Patents

Abstract

PURPOSE:To obtain the sensitive material contd. an anti-fogging agent having less tendency for generating lowering of sensitivity and deterioration of gradation by incorporating at least one of a specific compd. to the silver halide emulsion layer and/or an adjacent hydrophilic colloidal layer in the silver halide photographic sensitive material. CONSTITUTION:At least one of the compd. shown by formula I and at least one of the compd. shown by formula II are incorporated to the silver halide emulsion layer and/or the adjacent hydrophilic colloidal layer in the silver halide photographic sensitive material having at least one of the silver halide emulsion layer. In the formula, (n) is an integer of 2 or 3, and is a number of hydroxyl group, R<1> is hydrogen atom or halogen atom, R<2> is hydrogen atom or carboxyl group. The used amount of the compd. shown by formula I is preferably 1-1,000mg per 1mol of the silver halide, and that of the compd. shown by formula II is 50mg-10g, preferably 300mg-5g per 1mol of the silver halide respectively.

Description

[Detailed description of the invention]

3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic material, and particularly to a silver halide photographic material in which the generation of capri during storage of the photographic material is prevented. It's about materials. [Prior Art] Many anti-capri agents or stabilizers for silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) have been known. Typical examples include mercapto-directly substituted heterocyclic compounds, such as 1-722-ruyl compounds with a hydrophilic substituent, as described in U.S. Patent No. 3,266.897 and British Patent PA 1,257.201. 5-mercaptotetrazoles, acylamino-substituted 2-mercapto-1,3,4-triazoles as described in U.S. Pat. No. 4,264,721, as well as U.S. Pat.
Antifoggants of the type in which the mercapto groups of mercapto-substituted polycyclic compounds are blocked are disclosed in Japanese Patent No. 65,294, No. 3,615,617, and the like. In addition, as a heterocyclic compound having no mercapto group, 4-
Heptadoxy-6-methyl-1,3,3a,? - Poly-7zaindenes represented by tetrazaindene have also been used as stabilizers or antifoggants for a long time. Furthermore, many compounds other than heterocyclic compounds are known; for example, polyhydroxybenzene derivatives have been patented in the United States!
No. ¥43,236.652, Special Publication No. 43-4133,
It is described in No. 581441.3, etc. Furthermore, it is widely practiced in the art to use these conventionally known antifoggants in combination at a certain ratio. On the other hand, from the silver halide emulsion side of photosensitive materials, one technique for improving the image quality of photosensitive materials, which are constantly increasing in sensitivity, is to incorporate silver iodide into the silver halide composition, especially silver halide grains. There is also a known technique that utilizes the development suppressing effect of iodide ions released during development.Increasing the silver iodide content is preferable for increasing the sensitivity of photosensitive materials or improving image quality, but On the other hand, there is an undeniable drawback that the development inhibition effect of iodide ions is strengthened during development after image exposure, and the sensitivity is reduced. This results in a further decrease in sensitivity.Furthermore, photosensitive materials made of halogenated kite emulsions that have been specifically sensitized by increasing the iodine content cannot be stored over time - especially long-term storage under high temperature and high humidity conditions.
The increase in Capri or Ill! The deterioration of photographic characteristics such as softening of the tonality is significant. [Object of the Invention] The present invention has been made in light of the above-mentioned circumstances, and its first object is to contain an antifoggant that does not cause a decrease in sensitivity or deterioration of gradation due to development inhibition. The purpose of the present invention is to provide photosensitive materials. A second object of the present invention is to provide a photosensitive material containing an antifoggant that can maintain stable image quality when a photosensitive material consisting of a silver iodide-containing core/shell type silver halide 7L cut is stored over time. It is to provide. [Structure of the Invention] As a result of intensive research by the inventors, the above object of the present invention is to provide a photosensitive material having at least an IM silver halide emulsion layer.
The silver halide emulsion layer and/or the adjacent hydrophilic colloid layer contains at least one compound represented by the following general formula (+) and at least one compound represented by the following general formula [■] This was achieved through two steps. General formula (1) In the formula, Y is a hydrogen atom, a mercapto group, a hydroxy group, a nitro group, an amide group, an aliphatic group, an aromatic group,
It represents a heterocyclic group or a -COR group, and R represents an aliphatic group or an aromatic group. General formula [■] In the formula, n is an integer of 2 or 3 and represents the number of hydroquine groups, and the positions of the hydroquine groups on the benzene ring are 1, 2, 1, 3
．． 1.4 or 1.2.3. R1 represents a hydrogen atom, a halogen atom, an aliphatic group, or an aromatic group, and R2 represents a hydrogen atom, an aliphatic group, an aromatic group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a flukoxycarbonyl group, -COR ', -3O□Rco, -CQNIIR' or -NtlCQR'. Here, R3 and R4 each represent an aliphatic group or an aromatic group. However, R1 and R2 do not represent a hydrogen atom at the same time. 6 Furthermore, as a result of detailed studies, the inventors found that the silver halide emulsion layer has core/shell type silver halide grains with a higher silver iodide content in the core part than in the shell part, and that the silver halide emulsion layer has a total silver iodide content. It has been found that the effects of the present invention are more effectively exhibited in a photosensitive material comprising silver halide with a silver halide content of 0.1 to 10 mol%.The present invention will be described in more detail below. The compound represented by the general formula (1) (hereinafter referred to as the compound (1) of the present invention) is 1.2.3
．． It is a 4-thiatriazole type antifoggant. In general formula (1), the mercapto group represented by Y may be substituted, such as -SM (M represents an alkali metal atom such as sodium or potassium or an ammonium group), or a C1-C8 furkylthio group. (Methylthio group,
-propylthio group, hexylthio group, etc.), carbon number 3-8
Examples include phenylthio groups (propenylthio group, butenylthio group, etc.) or arylthio groups (phenylthio group, naphthylthio group, etc.). The hydroxy group represented by Y may also be substituted like the norcapto group. The amine 7 groups represented by Y may also be substituted, for example, the alkyl amine 7 groups substituted with an alkyl group having 1 to 8 carbon atoms (methyl amine/group, propyl amine 7 groups, etc.), noalkyl amide 7 groups (dimethyl amine 7 groups, dimethyl amine 7 groups, etc.). 7 groups), arylamine 7 groups substituted with an aryl group (anilino group, p
Examples include acylamide 7 groups substituted with an acyl group (acetamide group, benzamide group, etc.). The aliphatic group represented by Y″C may have a substituent, and examples thereof include a furkyl group, an alkenyl group, a cycloalkyl group, etc. The furkyl group preferably has a carbon number of 1
~8 (more preferably 1 to 6) linear or branched furkyl groups, such as methyl, ethyl, propyl, t
-butyl group, hexyl group, etc. The alkenyl group preferably includes an alkenyl group having 3 to 8 carbon atoms (more preferably 3 to 6 carbon atoms), such as a 7lyl group, a propenyl group, a butenyl group, and hexenyl 1&. The dichlorofurkyl group preferably includes a cycloalkyl group having 3 to 8 shells (more preferably 5 to 6 shells), such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. The aromatic group represented by Y may also have a substituent, and examples thereof include aryl groups such as 7-enyl group and naphthyl group. Examples of substituents that these aliphatic groups and Banko groups may have include halogen atoms, hydroxy groups, carboxyne groups, sia/groups, alkyl groups, alkenyl groups, aryl groups, alkoxy groups, aryloxy groups, Alkylami 7
group, 7 arylamides, 7 silamis, heterocycle IIi
, etc. The heterocyclic group represented by Y″C is preferably a 5- to 6-shell heterocyclic group having at least one nitrogen atom, oxygen atom, or sulfur atom, and may be fused with a benzene ring, and further includes the aliphatic group and It may be substituted with a substituent that the aromatic group may have.As the aliphatic group or aromatic group represented by Rr, Y″Ch
Groups similar to the aliphatic or aromatic groups represented can be mentioned. The compound of the present invention represented by the above general formula (1) can be easily synthesized by a known method, for example, by reacting inthiocyanates with hydrogen heptadide, or by reacting 5-chloro-1,2, The reaction of 3,4-thiatriazole with amines is applied. Regarding the synthesis method of these compounds,
Journal of the American Chemical Society (J, ^+n. Chew, Soc,), Volume 45, Page 2541 (
192:l), same magazine, vol. 47. 1916 pages (1925), same magazine, vol. 49, 2759r
T, (1927), same magazine, vol. 52, p. 1928 (19
30), Journal of Organic Chemistry, Volume 122, 441
Page (1957), same magazine, 26@, p. 1644 (
1981), same magazine, same volume, 5221 Shin (1961)
, Ber, DLacb, CI+cm, (
:es, )+ 294+ 249IQ (1891),
Same magazine, same volume, 2500 pages (1896), same magazine, 48
Volume 1833 (1915), Canadian Journal of Chemistry (Can,
J, Chew, ), vol. 35, 832
"N (1957), same magazine, 36@, p. 801 (1958), same magazine, vol. 37. Reference can be made to p. 101 (1959). Next, compounds used in combination with the compound (1) of the present invention The compound represented by the general formula [■] (hereinafter referred to as the compound of the present invention [
■). -・General formula [n) l: S3, R1, R2, R3 and the aliphatic group represented by (/I'?') may have a substituent, such as an alkyl group, an alkenyl group, etc. The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms (more preferably 1 to 18 carbon atoms), such as Ir methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group. The alkenyl group preferably includes an alkenyl group having 3 to 20 carbon atoms (more preferably 3 to 18 carbon atoms), such as an allyl group, a butenyl group, an octenyl group, a dodecenyl group, and an oleyl group. The aromatic group represented by R1-R4 may also have a substituent, and examples include a 7-aryl group, such as a 7-enyl group, a naphthyl group, etc. Examples of substituents that the aliphatic group and aromatic group may have include a halogen atom, hydroxy group, sulfo group, carboxy group, cyano group, ami7 group, furkyl group, alkenyl group, aryl group, alkokene group, and aryl group. Examples include an oxy group, an acyl group, a 7-silyl group, a 7-silami group, a 7-alkylamine group, a 7-arylamine group, an alkoxycarbonyl group, a 7-aryloxycarbonyl group, a carbamoyl group, a furkylcarbamoyl group, an arylcarbamoyl group, and the like. Examples of the salt of the carboxyl group or sulfo group represented by R2 include alkali metal salts (for example, lithium salts, potassium salts, etc.) and ammonium salts. , U.S. Patent No. tjS2,360.290, 2,7
01゜197, 2,728,859, 2,73
It is also possible to use compounds which can be obtained according to the synthesis method described in No. 2,300 or Pilstein I, and which are commercially available as antioxidants. Among the compounds [I] of the present invention, 5-7 nilino 1°2.3
．． I)E is a technique for using a 4-thiatriazole derivative as an antifoggant for color light-sensitive materials, and a technique for incorporating the derivative into a coupler to form an mDII coupler.
3307506^1. However, the above patent is clear! There is no suggestion in 1I18 that in combination with polyhydroxybenzenes, fogging of photosensitive materials during storage over time can be significantly reduced. In addition, if the silver halide emulsion used is a normal polydisperse type halide grain, the antifogging effect will be low, but in the present invention, the antifogging effect can be obtained for the first time with a core/shell type monodisperse silver iodobromide emulsion. There is no mention of such effects either. As stated above, the present invention combines at least one compound (+) of the present invention and at least one compound [■] of the present invention to form a silver halide emulsion, preferably a core/shell type monodisperse iodobromide emulsion. By adding these to the emulsion, stable photographic properties can be maintained even if the photographic material is stored for a long period of time. General formula [1] and general formula (I
Specific compound examples of I) are shown below, but the present invention is not limited thereto. Exemplified Compound [I] Exemplified Compound [■] OH The compound of the present invention can be used in conventional silver halide emulsion layers of light-sensitive materials, intermediate layers adjacent to the layers, filters JrIJ, antihalation layers, protective layers, undercoat waste, etc. It is contained in at least one of the constituent layers provided in the photosensitive material. A particularly preferred layer is a silver halide emulsion layer. The amount of the compound of the present invention to be added varies depending on the photosensitive material and the type of compound, but the compound represented by the general formula [1] is used in the range of 1 to 1,000 IIl& per mole of silver halide. is preferable, more preferably 5 to 300
i*g. The amount of the compound represented by the general formula (It) is 50 g to 10 g, preferably 8 to 5 g per 1 mole of halogenation. The ratio of compound (+) and compound (It) is 1:l by weight
O~1:500, more preferably 1:20~1:300
used in These compounds are dissolved in water or a hydrophilic organic solvent (meth/ol, acetone, etc.) and added to the required nitrifier. Further, in the case of a silver halide emulsion, it is added during chemical ripening, after chemical ripening, and/or immediately before coating the emulsion, but it is more preferably added at the end of chemical ripening of the silver halide emulsion. 1111 that does not impede the effects of the present invention! In II, known anti-capri agents or stabilizers outside the present invention can also be used. Anti-capri agents or stabilizers that can be used include:
For example, mercapto-substituted heterocyclic compounds such as benzothiazole, nitroingzole, penztriazole, and nitropencyimigzole as hepazoles! Examples of lIM include mercaptobenzimidazole, mercaptobenzoxazole, mercaptooxanoazole,
Mercaptoti7 noazole, Mercap)) Riazole,
Mercaptotriazine, mercaptotetrazole with 1-
phenyl-5-flucaptotetrazole), sulfonic acid groups or carboxy groups introduced into the above mercapto heterocyclic compounds, and azaindenes, such as 4
-Hydroxy-1.3.3a. Capri inhibitors or stabilizers well known in the art, such as 7-titrazaindene, can be used in combination. The core/shell type silver halide grains used in the present invention have a core portion consisting of silver halide containing silver iodide (C), and a content of silver iodide covering the silver iodide portion in the core portion. and a shell portion made of silver halide with a thickness lower than that of o. Silver halide grains having a diameter of oat to 0.1 μm are preferable. Preferred silver halide grains of the present invention include moderately halogenated grains having an average silver iodide content of 0.1 mol % or more and less than 10 mol %. The content of silver iodide in each of the core parts is preferably 60% or more, preferably 70% or more of the total, and the content of silver iodide in the shell part is preferably 0% or more and 40% or less. □ Silver halide grains in the present invention are preferably silver bromide as a silver halide other than the above-mentioned silver iodide. In this case, the content of silver chloride is approximately 1
Less than mol% is common. The shape of the silver halide grains according to the present invention is, for example, hexahedral, octahedral, dodecahedral, dodecahedral, icosahedral, plate-like,
It may be a spherical body, etc., and any of these various shapes may be used.
n. Although the particles may be interposed, octahedral, dodecahedral, dodecahedral, and icosahedral particles are preferable. At least one silver halide emulsion each having a silver iodide content in a specific range according to the present invention can be produced by coating monodisperse silver halide grains with a core part and a shell part. can. v! of the above core/shell type halogenated IT particles! Regarding the transmission method, for example, West German Patent No. 1,169.290,
British Patent No. 1,027,146, JP 57-154
No. 232, No. 59-52237, Special Publication No. 51-141
It is also stated in No. 7 etc. In the present invention, it is desirable that the silver iodide content in the R surface M (shell portion) of the silver halide grains having the above composition be as low as possible, and it is particularly preferably close to 0%. Furthermore, the inner core portion of the grains has a different content of silver iodide.
It may be formed as a layer of eJ or more. In addition, the difference in content between the layer with high silver iodide content and the layer with low silver iodide content is sharp 1
1'! ! 71! It may also have a boundary that is not necessarily clear and changes continuously. The distribution state of silver iodide in the above silver halide grains is as follows:
It can be detected by various physical measurements, and can also be investigated, for example, by measuring luminescence at low temperatures as described in the Abstracts of the 1986 Annual Conference of the Photographic Society of Japan. The silver halide emulsion used in the photographic light-sensitive material of the present invention is preferably an emulsion consisting of monodisperse silver halide grains, but other emulsions may be monodisperse or polydisperse. Here, what is meant by "monodisperse silver halide grains" as determined by an electron micrograph? When the L agent is observed, each silver halide grain appears uniform in shape and has a grain size distribution as defined by the following formula. In other words, if you divide the standard deviation S of the particle size distribution by the average particle size F″C″, is the value greater than or equal to 0.20? In the case of spherical silver halide grains, the average grain size referred to here refers to the diameter of the grains, and in the case of grains with shapes other than cubic or spherical, the average grain size refers to the diameter when the projected image is converted into a circular image of the same area. It is the average value of the diameter, and when the individual particle size is ``, and the number is 11., 2 is defined by the following formula.The above particle size is the above particle size. This can be measured by a variety of methods commonly used in the art for this purpose; a representative method is Loveland's "Particle Size Analysis Method"^, S. TlM, Transmission on Light Microscopy 1955, pp. 94-122 or Chapter 2 of [Theory of the Photographic Process] by Mies and Nohemes, 3rd edition, Macmillan Publishing Co., Ltd. (1966). . This particle size can be measured using an approximate value of the diameter of the projected area of the particle. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area. The relationship between grain size distribution is [between sensitometric distribution and grain size distribution in photographic emulsions! l! The Photographic Journal, Volume LXXIX, (1949-'
N 330-338 true This can be determined using the method described in the Tribelli and Smith paper. In addition, in the present invention, "the shape of the silver halide grains is uniform" means that the value determined from S/r of the above formula is 0°20 or less, and J'4: 0.2 to 0.2 for main fishing. A low density iodine emulsion with an average grain size of 0.5μ and 0.6 to 0.9
High iodine silver iodobromide with an average grain size of μ? The L agent is most preferred. The silver halide grains of the silver halide emulsion according to the present invention are
It is preferable that the above-mentioned monodisperse silver halide grains constitute at least 70% of all the grains in the same silver halide emulsion layer, and it is particularly preferable that all the grains are monodisperse silver halide grains. In addition, it is preferable to use core/shell type silver halide grains in which the core and shell have different silver iodide contents as the monodisperse silver halide grains. To produce a silver halide position of 1, grains of a desired size can be obtained by the Guprnoet method while keeping pAg constant. Further, highly monodisperse silver halide grains are disclosed in Japanese Patent Application Laid-Open No. 54-48521.
The method described in the above publication can be applied. For example, it is produced by a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing halogenated seed particles while changing the addition rate as a function of time. At this time, by appropriately selecting the time function of addition rate, pH, I crystal g, temperature, etc.
Highly monodisperse silver halide grains can be obtained. Next, the thickness of the shell portion covering the core portion must be thick enough not to hide the desirable qualities of the core portion, and conversely, be thick enough to hide the unfavorable qualities of the core portion. In other words, the thickness is limited to a narrow range defined by such upper and lower limits. Such a shell portion can be formed by depositing a soluble halide compound solution and a soluble silver salt solution on the core portion of Ilt-dispersible silver halide grains by a double noet method. The photosensitive material of the present invention can be applied to the following various types of photosensitive materials. For example, for general black and white, for X-ray recording, for plate making, for color printing, for color printing, for color paper, for color reversal,
Although it can be used for direct positive photosensitive materials, heat development photosensitive materials, etc., it is especially advantageous to apply it to color photosensitive materials with a multilayer structure. 'The silver halide emulsion of the present invention contains, as halide urine, silver bromide, silver iodobromide, silver iodochloride, nine chlorobromide, and silver chloride, which are commonly used in silver halide emulsions. Any one can be used. Silver halide grains used in silver halide emulsions are
It may be obtained by any of the acidic method, neutral method and ammonia method. The particles may be rlt long at one time,
The seed grains may be grown after they are grown. The method of creating the seed grains and the method of growing them may be the same or different. Silver halide emulsions are made by mixing halide ions and silver ions at the same time. However, one may be mixed in a solution in which the other is present.Also,) 7% lodenide ions and silver ions may be mixed in a pot while considering the critical growth rate of lodenide crystals. It may also be produced by sequentially and simultaneously adding g to the pH and/or p of By this method, silver/10 denride grains with a regular crystal shape and nearly uniform grain size can be obtained. After growth, the halogen composition of the particles may be changed using a component method. Halogen Kitamoto emulsion is produced by using a silver halide solvent as necessary during production to adjust the grain size of silver halide grains.
Particle shape, particle size distribution and particle growth rate can be controlled. During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( At least 1 selected from (including complex salts)! By adding metal ions using gi, these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, they can be added inside the particles and/or on the particle surfaces. Reduction-sensitizing nuclei can be added to the endorsement. The silver halide emulsion may be used to remove unnecessary soluble salt deposits after the growth of silver halide grains is completed, or may be left to contain the salts. Researeh D'1
selosure (hereinafter abbreviated as RD) can be carried out based on the method described in Section 1 of No. 17643. □゛Silver halide emulsion M may be a mixture of two or more silver halide emulsions formed separately. can. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a liquid metal sensitization method using a noble metal compound of Kanasoike, etc. can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. Sensitizing dyes may be used alone, but 2+! I
A dye that does not have a spectral sensitizing effect by itself along with a sensitizing dye, or a compound that does not substantially absorb visible light, which may be used in combination with sensitizing dyes and above, and a strong color that enhances the sensitizing effect of the sensitizing dye. A sensitizer may also be included in the emulsion. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holobolane 7-nin dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used. Particularly useful pigments include cyanine pigments, melonanine pigments,
and a complex melonanine pigment. This C) color 71
Any of the nuclei commonly used in cyanine dyes can be used as the basic An ring nucleus. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and the nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and these Aromatic hydrocarbon in the core7. Nuclei with fused rings, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, penzimiguzole nucleus, quinoline branch etc. These nuclei may be substituted on carbon atoms. Merocyanine dyes or synthetic merocyanine dyes include a pyrazolin-5-one nucleus, a thiohyguntoin nucleus, and a 2-thioxacillinone-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolinone-2,4-dione nucleus, logenine nucleus, thiobarbic acid nucleus, etc. can be applied. Useful sensitizing dyes used in the blue-sensitive halogenated 11fL agent layer include, for example, Seishi Tokkoku l'F No. 929.080.
No. 2,231.658, U.S. Patent No. 2,493.
No. 748, No. 2.503,776, No. 2,519.0
No. 01, No. 2,912.329, No. 3, 656,
No. 959, No. 3,672,897, No. 3,694,2
No. 17, 4,025. J49 No. 4, 0i 6, 5
No. 72, British Patent No. 1,242.588, Special Publication No. 1972
-14030, No. 52-24844S; etc. can be mentioned. Sensitizing dyes useful in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 8, No. 2,739,149, 1 Tsukasa 2,945.76
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in R. No. 3 and US Pat. No. 505.979. Additionally, useful sensitizing dyes for use in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 4, No. 2,270,378, No. 2,442.710
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in Japanese Patent No. 2,454.629, No. 2,776.280, and the like. Furthermore, U.S. Patent No. 2.213,9
No. 95, No. 2,493,748, No. 2,519. OO
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 1, German Patent No. 929.080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. The representative/front side is Tokuko No. 43-4932, No. 43-4933, No. 4
3-49'J6, 44-32753, 45-2
58: (No. 1, No. 45-26474, No. 46-116
No. 27, No. 46-18107, No. 47-8741,
No. 47-11114, No. 47-25379, No. 47
-37443, 48-28293, 48-38
No. 406, No. 48-38407, No. 41-38408
No. 48-41203, No. 48-41204, No. 49-6207, No. 50-40662, No. 53-1
No. 2375, No. 54-34535, No. 55-1569
No. 50-33220, No. 50-33828, No. 50-38526, No. 51-107127, No. 51-115820, No. 51-135528, No. 5
No. 1-151527, No. 52-23931, No. 52-
No. 51932, No. 52-104916, No. 52-10
No. 4917, No. 52-109925, No. 52-110
No. 618, No. 54-80118, No. 56-25728
No. 57-1438, No. 58-10751, No. 58
-91445, 58-153926, 59-1
1453:1, 59-116645, 59-1
No. 16647, U.S. Patent No. 2,688,545, U.S. Pat.
, No. 977.229, same: 1. : 197°060, 3,506.443, 3,578.447, 3
, No. 672+898, No. 3,679.428, No. 3,
769,301, ibid., 814. No. 609, No. 3, No. 837, and No. 862. Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic isoacid formaldehyde 1 condensation. products (e.g., U.S. patent r
:tS3,471.510)), azaindene compounds described in Cadmiuni, aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (for example, U.S. Patent No. 12,9
Nos. 33,390 and 3,635,721). U.S. Patent No. 3,615.613, 3
, No. 615,641, No. 3,617,295, No. 3,
The combinations described in No. 635.721 are particularly useful. Silver halide polishing is used during chemical ripening, at the end of chemical ripening, and for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of photosensitive materials, or to maintain stable photographic performance. / Or silver halide after chemical ripening? L
Compounds known in the photography industry as anti-capri agents or stabilizers can be added prior to applying the shavings. As antifoggants and stabilizers, US Patent No. 2゜713
．． No. 541, No. 2,743.180, No. 2,743.
Pentazaindenes described in U.S. Pat. No. 181, U.S. Pat.
, No. 444,605, No. 2,756゜147, No. 2+
No. 8415+581, 2,852. : No. 175, RD
7 zaindenes such as the tetrazaindenes described in No. 14851, the triazaindene group described in U.S. Pat. ; U.S. Patent No. 2,131,038, No. 3,342,596;
Thiazolium salt described in No. 3,954.478,
Quaternary onium salts such as pyrylium salts described in U.S. Patent No. 53.148°067 and phosphonium salts described in Japanese Patent Publication No. 50-40665;
, 403, No. 927, No. 3,268゜897, No. 3
, 708, 303, mercaptotetrazoles, mercaptotriazoles, and mercaptonoazoles described in JP-A-55-135835 and JP-A-59-71047; Mercaptodiazoles, US Patent i11't3,3
97.987, mercaptobenzothiazoles, mercaptobenziimiguzole, U.S. Pat.
Mercapto-substituted heterocyclic compounds such as the mercaptooxanoazoles described in US Pat. 236.652, kanafurs described in Japanese Patent Publication No. 43-10256, resorcinols described in Japanese Patent Publication No. 58-44413, and gallic acid esters described in Japanese Patent Publication No. 41-4133. polyhydroxybenzenes; tetrazoles described in West German Patent No. 1.189.380, trifyl-ols described in U.S. Pat. No. 3,157.509, U.S. Pat. No. 2,704.721 Benzotriazoles described in US patent fjSL287
．． No. 135, the urazoles described in U.S. Patent No. 3.
pyrazoles described in US Pat. No. 106,467, indazoles described in U.S. Pat. No. 2.271.229,
and 7zoles such as polymerized benzotriazoles described in VF Patent No. 59-90844 and U.S. Pat.
, 161.515, the 3-pyrazolidone derivatives described in U.S. Pat. a Heterocyclic compounds such as lydone; Special 1jt (IM (54-
No. 130929, No. 59-137945, No. 1404
Various inhibitor precursors described in U.S. Pat. No. 45, U.K. 1, U.K. Pat.
Sulfinic acid and sulfonic acid derivatives described in No. 047.393; □U.S. Pat. No. 2,556,263,
Same 2. C19,405, 2゜488.709, 2,728.60: (There are inorganic salts, etc. recorded in the No. C19,405, 2゜488.709, 2,728.60. It is best to use gelatin, but
Hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and polymers, other proteins, sugar derivatives, cellulose conductors, and synthetic hydrophilic polymeric substances such as single or copolymers can also be used. The photographic emulsion layer and the hydrophilic colloid layer of the light-sensitive material of the present invention contain one or more Pine Gu (or protective colloid) molecules.
Hardening can be achieved by using one or more hardening agents that increase the strength of the A-bridged film. Hardener is at F! ! It is not necessary to add a hardening agent to the solution, but it can be added once the photosensitive material is hardened. ! It is also possible to add hardeners to the liquid. A plasticizer can be added to the silver halide 7L layer and/or the hydrophilic colloid layer of the photosensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in Section Xn-8 of RD 17643. The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials contain water-insoluble or water-insoluble materials for the purpose of improving dimensional stability.
It is possible to contain a dispersion (Latenx) of synthetic polymers. In the emulsion layer of a light-sensitive material, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, 1]-phenylenenoamine derivative, amine/phenol derivative, etc.) during color development processing. A dye-forming coupler is used. The dye-forming couplers are different from each other? It is common to select a dye that absorbs light in the photosensitive spectrum of the TL agent layer for the L-abrasive layer, and is blue-sensitive? L
A yellow dye-forming coupler is used in the ablation layer, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, these dye-forming couplers require reduction of four molecules of silver ions in order to form one molecule of dye4? It may be either P-quantity or bi-isomerism, in which only two molecules of silver ions are reduced. Dye-forming couplers can be used as development inhibitors, development promoters, whitening promoters, developers, sub-halogenated solvents, toning agents, hardeners, capri agents, and fogging agents by coupling with the oxidized form of the developing agent. Compounds that release photographically useful fragments such as inhibitors, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. Instead of the DIR coupler, a DIR compound which undergoes a cuff-pulling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used. DIR couplers and VDIR compounds that are controversial include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached at the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( These include timed DIR couplers and timed I) IR compounds. Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination with dye-forming couplers. As the yellow dye-forming coupler, known acyl 7cetanilide couplers can be preferably used. Among these, benzoyl 7ceto7nili and pivaloyl 7cetanilide compounds are preferred. Examples of magenta dye-forming couplers include 5-pyrazolone couplers, virazolobenlimigsol couplers, and Kai! i7 sylacetonitrile couplers, ingzolone couplers, etc. can be used with the couplers of the present invention. As the cyan dye-forming coupler, a 7-er/- or 7-tole coupler is generally used. Dye-forming couplers that do not need to be attached to the surface of halogenated crystals, D[R couplers, DIl+ compounds, image stabilizers, color anti-capri agents, etc. Hydrophobic compounds are processed using solid dispersion method, latex dispersion method, etc.
Dispersion can be performed using various methods such as oil-in-water emulsion dispersion method, which is a method for dispersing hydrophobic compounds such as couplers.
Depending on the structure, etc., it is possible to select the value of jΔ. oil in water 4
The color type 7 fractionation method separates hydrophobic additives such as couplers.
Conventionally known methods can be applied, and usually the boiling point is about 15
A high boiling point organic solvent of 0°C or higher is used in combination with a low boiling point and/or water-soluble organic solvent if necessary, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution with a stirrer, It may be emulsified and dispersed using a homonizer, a colloid mill, a 7O-)7 mixer, an ultrasonic two-layer device, etc., and then added to the desired hydrophilic colloid liquid. After or at the same time as dispersion, a step of removing a low-boiling, α-organic solvent may be included 4. High boiling point; 1: As a medium, a phenol derivative that does not react with the oxidized form of the developing agent, an alkyl ethyl heptatarate, or phosphoric acid. Organic solvents having a boiling temperature of 150° C. or higher, such as esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, are used. Low boiling or water soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, bunal 7-cetate F, butyl acetate, chloroform, carbon tetrachloride, di[romethane, nitroethane, benzene, etc.]; Examples of organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol,
Acetonitrile, nooxane, trimethylformamide,
Examples include trimethyl sulfoxide, hexamethylphosphoric triamide, noethylene glycol 7/phenyl ether, and phenoxy ethanol. When dye-forming couplers, DIR couplers, DIR compounds, image stabilizers, color anti-capri agents, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, hydrophilic colloids can be used as alkaline aqueous solutions. It can also be introduced inside. Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color anti-capri agent can be used to prevent graininess from showing off. The rich color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer. The light-sensitive material using the silver halide emulsion of the present invention can contain an image stabilizer to prevent deterioration of the dye image. Examples of image stabilizers include phenol conductor and its bis form, hydroxycuturane and its su form, hydroxychroman and its human pia form, piperinone derivatives, aromatic amine compounds, pendinooxane derivatives, pen X dioxole derivatives, and silicone. Atom-containing compounds, thioether compounds, etc. are preferred. Specific examples include British Patent No. 1.410゜846, VT 49-134326, VT 52-35633, 52-147434, 52-150630, 54-145530, 5
No. 5-6321, No. 55-21004, No. 55-12
No. 4141, No. 59-3432, No. 59-5246, No. 59-10539, Special Publication No. 48-31625,
JQ No. 49-20973, No. 49-20974, No. 50-23813, No. 52-27534, U.S. Patent No. m 2,418,613, I! t710+801, 2,735+765, 2,816.028,
3,069,262, 3,336,135, 3,432.300, 3,457,079,
(No. 573,050, No. 3,574,627, No. 3
, No. 698.909, No. 1, No. 700,455, No. 3
, No. 764,337, 3,935,016%, 1Fi
13+982,944, 4,013,701, 4,113.495, 4,120,723, 4
, No. 155,765, No. 4,159,910, No. 4,
254.216, 4, 268, 593, 4
, No. 279.990, No. 4,332,886, No. 4,
No. 360,589, No. 4,430,425, No. 4,4
No. 52,884 and the like. Preservation of the photosensitive material of the present invention, 4/i! I. Hydrophilic colloid layers such as the intermediate layer may contain an ultraviolet absorber to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or the hydrophilic colloid layer of the photosensitive material. A compound preferably used as a development accelerator is RD170.
The compound is a compound described in Section XXI B to D of No. 43, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes. The emulsion layer of the light-sensitive material contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, improving film stability, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like. Optical brighteners are used in photosensitive materials to emphasize the whiteness of the white background and to make the coloring of the white background less noticeable. Compounds that can be preferably used as fluorescent sensitizers are described in item 7 of I'tl) No. 17643. The photosensitive material can be provided with a filter/L antihalation layer and an auxiliary layer for the iranoation prevention layer. These layers and/or the 7L layer removal layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Such dyes include oxonol dyes, hemioxonol dyes, and styril! 0 dye, melonanine dye, cyanine dye, azo dye, etc. The halogenated kite emulsion layer and/or other hydrophilic colloid agents of the photosensitive material reduce the gloss of the photosensitive material, improve processability,
A matting agent can be added to prevent photosensitive materials from sticking together. A lubricant can be added to the photosensitive material to reduce sliding friction. Tsu1 for photosensitive material? An antistatic agent can be added for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the non-layered side of the support. It may be used in a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated with respect to the L layer and/or the support. Preferably used antistatic coatings are the compounds described in ID 17643 No. XII. The photographic emulsion layer and/or the hydrophilic colloid layer of the light-sensitive material include coating properties, antistatic properties, slip properties, emulsification and dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (promotion of development, high contrast, sensitization, etc.). The support used in the photosensitive material of the present invention includes a flexible reflective support such as paper laminated with an a-shaped fin polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer!4:), etc., or synthetic paper. , films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc., and flexible supports in which these films are provided with reflective layers; Includes glass, metal, ceramics, etc. The hydrophilic colloid layer of the photosensitive material can be applied directly or after applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, or to improve the adhesion, antistatic property, dimensional stability, and abrasion resistance of the support surface. It may be coated through one or more subbing layers to improve properties such as hardness, hardness, antihalation, frictional properties, and/or its properties. When coating the photosensitive material, a thickener may be added to improve coating properties. Also, for things like hardeners, which are so reactive that if added to the coating solution in advance, they will cause delta before coating, it is best to mix them onto the surface of the coating using a static mixer or the like. preferable. As a coating method, extra thin coating and curtain coating, which allow two or more types of coatings to be applied at the same time, are particularly useful, but packet coating may also be used depending on the purpose. Also, the coating speed can be selected arbitrarily.
be able to. The light-sensitive material of the present invention is exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon 7
- Data lamps, xenon 7-laser lamps, cathode ray tube flying spots, various field lamps, light emitting lights, electron beams,
Any known light source can be used, including those emitted from phosphors excited by XFA, gamma rays, alpha rays, and the like. The exposure time is not only the 1 millisecond to 1 second exposure time normally used with cameras, but also short exposure times of 1 microsecond, such as 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. Furthermore, it is possible to perform exposures for more than 1 second. Even if double exposure is done continuously,
It may be performed intermittently. C) A known method is used to develop the photosensitive material of the present invention. Place J! l! The temperature used is between 18.degree. C. and 50.degree. C., and depending on the purpose, either black and white photographic processing, lithographic development Pl or color photographic processing in which a dye image is to be formed are applied. - In white photographic processing, the developing agents are nohydroxybenzene M (e.g. hydroquinone), 3-pyrazolidone (
For example, 1-phenyl-3-pyrazolidone), 7-methyl/7-ols (for example, N-methyl-p-7 minophenol), and ascorbic acid can be used in combination. The developing solution contains a well-known preservative, an alkaline agent, and pI
Contains a t-buffer, a capri inhibitor, etc., and further contains a solubilizing agent, a toning agent, a development accelerator, a surfactant, an antifoaming agent, etc. as necessary.
It may also contain water softeners, hardeners, etc.-1. The present invention can also be applied to so-called developer-containing type photosensitive materials in which a developing agent is contained in the photosensitive material and processed in an alkaline solution. Next, when forming a dye image, an alkaline aqueous solution containing a color developing agent is used. As the color developing agent, a known primary aromatic amine developer such as a phenylenenoamine developer can be used. Color developers also contain alkali metals such as sulfites, carbonates, borates, and phosphates.
It may contain a salt, a halogen salt, an organic anti-capri agent, a water softener, a preservative, an organic solvent such as benol alcohol and ethylene glycol, a development accelerator such as a quaternary ammonium salt, and an amine. . Processing after color development is usually a bleaching process. The bleaching solution may be used at the same time as the fixing process or separately.
), compounds of polyvalent metals such as chromium (IV), copper (rl), persulfur m\R, etc. are used. For example, 7-erocyanide, dichromate, iron, cobalt salt, ethylene-7minetetraacetic acid, nitrilo) +
7 Acetic acid, persulfate, permanganate, etc. can be used.

【Example】

The present invention will be explained in more detail with reference to Examples below. Example 1 A monodisperse silver iodobromide core/shell type emulsion with octahedral crystals and an iodobromide core/shell type emulsion with octahedral crystals and an iodobromide emulsion for comparison were prepared by the double noeft method according to the method described in Jikai Publication No. 57-154232 and the method of Ii vA. The silver bromide polydisperse twin emulsion was prepared as follows:
Eight types were prepared as shown in the table. Upgrade S to the above! ! Each emulsion that was made, respectively! After carrying out the sensitization method using ``LL most chemical sensitization (salt-containing and sulfur sensitizer), the compounds represented by the general formulas [I] and [11] according to the present invention are added as shown in the m2 table, respectively. After sufficient adsorption (C), appropriate amounts of saponin as a coating aid and formalin as a hardening agent were added to each 7L agent. A sample of 26 iq1 was prepared by uniformly coating the solution at a concentration of 4011 Ig/dm2.The samples prepared as above were made into 7-recipe samples, which were left at room temperature for 3 days, and at a temperature of 55°C and a relative humidity of 7%.
3 days below and 3 days below temperature 50℃ relative humidity 80%
A time-lapse sample with a strong $11 deterioration was prepared after being left for 1 day. Thereafter, normal sensitometric exposure was carried out, and then the film was subjected to sensitometric exposure at 35° C. for 30 hours using the following processing solution (A), and then washed with water and dried to measure the sensitivity. Processing liquid IA1 (Developer for black and white photosensitive materials) 1-phenyl-3-pyrazolidone 1.5g Hydroquinone 30°5-nitroingzole 0.25g Potassium bromide
5g anhydrous sodium sulfite
55H potassium hydroxide
30ggA acid
10g Glutaraldehy 1″ (25%)
Add 5g of water to bring the total amount to 19. The results obtained are shown in Table 2 below. However, the fog value indicates the value obtained by subtracting the base density, and the sensitivity value is expressed as a relative sensitivity from the sensitivity at the fog value + 0.5 position, with the comparison sample set as 100. The comma indicates the linear part on the characteristic curve. Indicated by slope. As is clear from Table 2 above, Sample 6 according to the present invention.
7.8.9 and V22, despite the harsh storage conditions,
It can be seen that the occurrence of capri and gamma deterioration are suppressed, and the stability of the film during storage is improved. Example-2 Emulsion F (present invention) prepared in Example-1 and Emulsion H (1) (
Comparison) was chemically aged with gold and sulfur sensitizers to maximum sensitivity. Next, an appropriate amount of 5,5'-no7-di-9-ethyl-3,3'-no-γ-sulfopropyloxacarposi7-2 sodium salt was added as a green-sensitive sensitizing dye, and green-sensitive halogenated A silver emulsion was prepared. Then, per mole of silver mihalide, magenta coupler -
as, 1-(2,4,6-trichlorophenyl)-3
-[3-(2,4-not-7mil7eth/xy7set7
1-(2,4,6-trichlorophenyl)-4-(1-su7tylazo)-3-(
Weighed 2.5 g of 2-chloro-5-octadecenylsuccinimide (7nilino)-5-pyrazolone, and then added 120 g of triphrenorphosphate, 24 g of ethyl acetate.
0 mj) was mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triimpropylnaphthalene sulfonate and 550 l of a 7° 5% aqueous gelatin solution was added to the above emulsion. This emulsion was divided into 21 parts, a comparative compound and a compound according to the present invention were added in combination as shown in the third column below, and after sufficient adsorption, 2-hydroquine-4 was added as a gelatin hardener. , 6-nochlorotrianone sodium were uniformly added to prepare a silver halide emulsion. This emulsion is mixed with 3. A sample was obtained by uniformly coating and drying on a triacetate film that had been subbed so as to achieve Og/s2 (No. 27-47). The obtained film sample was subjected to the same forced deterioration test as in Example 1, then wedge exposed in the usual manner, and color developed according to the following color processing steps. The color sensitometry results obtained from the obtained pieces are shown in Table 3 below. The philtrum fog is the value after subtracting the base concentration, and the sensitivity is based on the blank sample left for 3 days (sample No. 27).
) is expressed as 100. or,
Gamma is expressed by the slope of the straight line. Processing process [Processing temperature 38°C] Processing time Color development 3 minutes 15 seconds Bleaching
Wash with water for 6 minutes and 30 seconds
3 minutes 15
Fix in seconds Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows:
be. [Color developing solution] 4-7mi/-3-methyl-N-ethyl-N-(β-hydroxyethyl)-7niline sulfate 4.75゜anhydrous autoI giant sulfuric acid tri-num
4゜25F1 hydroxylamine 1/2 sulfate 2. Q. Anhydrous potassium carbonate 37.5g
Change 1

1.3g Nitrilotriacetic acid, 3S F lium salt (monohydrate)
2.5g Potassium hydroxide Add 1.0g water to make 1q, adjust pH to 6 using sodium hydroxide.
ni3!4#i! do. [Bleach] Ethylenenoamine titraacetic acid iron ammonium salt
1
00,0゜Ethylenenoaminetitraacetic acid diammonium salt
10. Ammonium O-bibromide
150. Og hydroxyl acid
Add 10.0 g of water to make [Q], and adjust the pH to 6.0 using ammonium water. [Fixer] Ammonium thiosulfate 175.0° Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make IQ, and use acetic acid to make pf! 6. Ql: Adjust. [Stabilizing liquid] Formalin (37% aqueous solution) 1.5J Funigtsux (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5+n (
1 Add water to make 19. As is clear from Table 3 above, the compounds according to the present invention [
Sample 30, 33.36 by combination of l) and ([1)
and No. 39, no deterioration of photographic properties was observed due to storage over time. Example 3 A multilayer color photosensitive material sample (comparison) was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support. However, for silver halide 7L polishing, a monodisperse silver iodobromide core/shell type emulsion according to the present invention was used. 1st WJ: Antihalation layer Black gelatin layer containing colloidal silver 2nd layer: 1t11ffl M Gelatin layer 3rd /l'l: Red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion
Silver iodide: 5 mol% (average grain size 0.64 μm) Silver coating amount: 1.79 g/11” Sensitizing dye 1: 6 x 10 per mol of silver
-'molar sensitizing dye ■...2 x 10 per mole of silver
-S mole coupler A...O per 1 mole of silver, OSS mole coupler-...0.003 mole per 1 mole of silver Coupler D......For 1 mole of silver 0.003
03 mol triphrenol phosphate-tt cloth fiO, 3a+
t'/m2 4th layer: red-sensitive high-sensitivity emulsion layer silver iodobromide? LJ'llll Formation 1 [: 4 mol% Average particle size 0.62μ Theory Silver coating amount... Bow, 4 g 7 m' Sensitizing dye 1... 1 o 3 X t per mole
o-' mole sensitizing dye J...1.2X 1 for it mole
0-5 mole coupler F...0.0125 per mole of silver
Molar coupler C...0.0016 per mole of silver
Moltrifrenorphosphate application amount 0.2+at'h1 Fifth! i: Intermediate layer Same as second layer Sixth layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Iodide jll: 4 mol% and average grain size 0.
62μ Coating amount of silver: bow, Og/+o2 Sensitizing dye ■: 3X per mole of silver 10-
'Molar sensitizing dye■・・・・・・Left t to fi1 mole and IX 1
0-'mol h 7' Ra-B...0.0 per mole of silver
8 mole coupler M...ff o, oo for 11 moles
s mole coupler D...0.00 for ff11 mole
15 mol triphrenor phosphate application amount 1.4+a//+Ω2? tS7 layer: green layer green sensitive high sensitivity emulsion layer silver emulsion ta iodide: 5 mini 5 molar grain size 0.
64μ+n Silver coating amount...Archie-6g/la2 Sensitizing dye ■...2.5X per mole of silver 1
0-'Mole sensitizing dye■...O, sx 1 per mole of silver
o-5 mole coupler B...0.02 mole per mole of silver Coupler M...0.003 mole per mole of silver triphrenorphos 7 Coating amount 0,' 8m1/m2 8th layer: Yellow filter single layer gelatin layer containing light color Floyd silver in gelatin aqueous solution. 9th layer: 14T sensitivity, low sensitivity 7L agent)a Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.
7μm Silver coating amount...0.5g/...2 Coupler Y...0.12 per 11 moles of fi
5 mol triphrenor phosphate) fl cloth fitO, 3Io
1/+2 10th I level: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.8
μl Silver coating amount: 0.6 g/m” Coupler Y: 0.04 mol of tricresolphos 7A per 1 mole of silver)! Fabric amount: 0.11#l/l112 !l'S11 layer: Protective layer polymethyl methacrylate particles (diameter 1.5μIfi)
Apply gelatin (1) containing gelatin.For the coupler of each layer, add the coupler to a solution of trifrenor phosphate and ethyl acetate, add sodium p-dodecylbenzenesulfonate as an emulsifier, and dissolve by heating.
The mixture was mixed with a heated 10% gelatin solution and emulsified using a comid mill. In each layer, a gelatin hardener and a surfactant were added to the above composition. The sample prepared as described above was used as a blank sample for 4 days. Compound used to make the sample. Sensitizing dye I: Anhydro 5,5'-nochloro 3.3
'-7-(γ-sulfopropyl)-9-ditylthiacarbocyanine hydroxide pyrinium salt sensitizing dye ■: Anhydro-9-ethyl-3,3'-(
γ-sulfoprovir)-4,5,4',5'-nobenzothiacarbosia, ninhydroxide triethyl superamine salt sensitizing dye ■: Anhydro-9-ethyl-5,5'-
Fucrolo 3,3'-di(arsulfoprovir) oxacarbocyanine hydroxide sodium salt sensitizing dye ■: Anhydro 5.6.5',6'-tetrachloro-1,1'-diethyl-3,3 ′−di(β−[β
-(γ-Sulbopropoxy)ethoxy]ethylimidazolocarposi7ine hydroxide sodium saltも, Below, \l Coupler D Coupler F +111 a Coupler Y The above-mentioned halogen I? , the third layer which is silver milk n++ and the fourth layer
The red-sensitive layer of the layer and the 67ii1. After adding a sensitizing dye to the seventh green-sensitive layer, the ninth layer, and the first O-layer blue-sensitive layer, a comparative compound and a compound of the present invention were added as shown in Table 4 below. A combination of [I] and CI) was added, adjusted and multilayered to create 5 types of samples (No. 4).
9-53). In addition, as another comparison sample, a polydisperse non-core/shell emulsion (comparison emulsion) prepared with the same average grain size as the silver iodide emulsion described above (comparison emulsion) was coated in a similar manner. Five types of samples were created (No. 54-'58). The obtained multilayer color photosensitive material sample was left for 30 minutes at a temperature of 55° C. and a relative humidity of 7% as in Example 2 as a heat resistance forced deterioration test, followed by normal wedge exposure. The same color processing was performed. The results are shown in Table 4. The results of the storage test on each layer in Table 14 also show that the combination of the compounds according to the present invention provides a fog suppressing effect with less desensitization and no deterioration of photographic properties even in multilayer color light-sensitive materials.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer, a compound represented by the following general formula [I] is contained in the silver halide emulsion layer and/or the adjacent hydrophilic colloid layer. and at least one compound represented by the following general formula [II]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y is a hydrogen atom, a mercapto group, a hydroxy group,
Nitro group, amino group, cyano group, aliphatic group, aromatic group,
It represents a heterocyclic group or a -COR group, and R represents an aliphatic group or an aromatic group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc.
3, 1, 4 or 1, 2, 3. R^1 represents a hydrogen atom, a halogen atom, an aliphatic group, or an aromatic group, and R^2 represents a hydrogen atom, an aliphatic group, an aromatic group,
Carboxy group or its salt, sulfo group or its salt, alkoxycarbonyl group, -COR^3, -SO_2
Represents R^3, -CONHR^4 or -NHCOR^4. Here, R^3 and R^4 each represent an aliphatic group or an aromatic group, provided that R^1 and R^2 do not represent a hydrogen atom at the same time. ] (2) The silver halide grains of the silver halide emulsion layer are core/shell type silver halide grains having a higher silver iodide content in the core part than in the shell part, and the total silver iodide content is 0. The silver halide photographic material according to claim 1, characterized in that it comprises 1 to 10 mol% of silver halide.