JPS6046696B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material which has a high frequency range, has little fogging, and is capable of obtaining stable photographic properties.

More specifically, it is a high-sensitivity silver halide photographic light-sensitive material that can suppress the occurrence of fog even if it uses polyalkylene oxide compounds that give extremely effective properties to silver halide photographic light-sensitive materials. Regarding. In recent years, demands have become increasingly complex and diverse regarding the performance of silver halide photographic materials, and in particular, silver halide photographic materials with stable photographic performance and high to ultra-high sensitivity are required. .

In particular, in the case of X-ray photosensitive materials, in order to reduce the amount of X-rays that the human body is exposed to, it is necessary to have high sensitivity so that more information can be obtained with a smaller amount of X-rays, and stable photographs with less fogging. Photosensitive materials are required. Conventionally, one of the methods to increase the sensitivity of silver halide photographic materials is to
For example, the theory of the photographic process.
phicprocess), (1967) 3rd edition, P.
It is said that it is extremely effective to incorporate a polyalkylene oxide (especially polyethylene oxide) type compound into a silver halide photographic light-sensitive material as described in No. 369-370.

In addition to its purpose as a sensitizer, it can also be used to prevent damage caused by static electricity in photosensitive materials (e.g., the formation of static marks, etc.).
Antistatic agents have been used for the purpose of preventing dust collection, etc., and there have been many reports that polyalkylene oxide compounds are extremely effective for this purpose as well. Furthermore, a photosensitive layer constituting the photosensitive material,
There have been many reports on the use of polyalkylene oxide surfactants for the purpose of achieving uniform coating properties of coating films such as protective layers. As described above, polyalkylene oxide compounds are compounds that provide extremely effective properties to silver halide photographic materials, but there are significant restrictions on their use.

That is, if an amount exceeding a certain limit is used, fog increases and photographic properties are significantly deteriorated. This phenomenon occurs when the silver halide photographic material is dried at low humidity and at high speed during the production process, or when the film is stored under harsh conditions at high temperature and high humidity after production. It is particularly noticeable in the United States and has become a serious problem. Further, in a light-sensitive material having a light-sensitive emulsion layer using silver iodobromide as the silver halide, when a polyalkylene oxide compound is contained, the sensitivity becomes extremely high, but fogging occurs significantly.

In particular, due to the demand for rapid processing of X-ray photosensitive materials, polyalkylene oxide is used in such X-ray photosensitive materials because they are rapidly developed at high temperatures using high-PH developing solutions containing aldehyde-based hardeners. System compound. When the material is added, the result is an increase in fog. In this point,
Regarding methods for suppressing fog in silver halide emulsions and silver halide emulsions containing polyalkylene oxide compounds,
Numerous reports have been made to date. like this! Typical fog inhibitors include, for example, 4-hydroxy-6-methyl-1-3-C-7-tetrazaindene and 1-phenyl-5-mercaptotetrazole. It is not possible to obtain a sufficiently stable fog suppressing effect under the current manufacturing and developing conditions of photosensitive and photosensitive materials, and increasing the amount added in order to obtain a fog suppressing effect lowers the sensitivity. This usually results in a decrease or softening of the tone, resulting in undesirable results. Therefore, there is a need for the emergence of an appropriate blurring inhibitor that can overcome the above-mentioned drawbacks by using polyalkylene oxide compounds in a high-sensitivity silver halide photographic light-sensitive material using silver iodobromide. Currently, there is a strong demand for this. The first object of the present invention is to prevent the occurrence of fogging even when a polyalkylene oxide compound that provides extremely effective properties to a silver halide photographic light-sensitive material using silver iodobromide is used in sufficient quantities. It is an object of the present invention to provide a highly sensitive silver halide photographic material that can suppress the oxidation and obtain stable photographic properties.

A second object of the present invention is to add a fog suppressant to suppress the occurrence of fog in a silver halide photographic light-sensitive material using a silver iodobromide photographic emulsion containing a polyalkylene oxide compound. There is also provided a high-sensitivity silver halide photographic material containing silver halide in a constituent layer. The third object of the present invention is to provide a high-sensitivity silver halide silver halide with low fogging even when rapid processing is performed at a high temperature using a high pH developer containing an aldehyde hardener. An object of the present invention is to provide photographic materials.

A fourth object of the present invention is to suppress the occurrence of fog even when drying at high sensitivity and high speed when producing silver halide photographic materials containing silver iodobromide and polyalkylene oxide compounds. The object of the present invention is to provide a silver halide photographic material that can be used.

A fifth object of the present invention is to ensure that silver halide photographic materials containing polyalkylene oxide compounds have high sensitivity even when stored for long periods under harsh conditions at high temperatures and high humidity. It is an object of the present invention to provide a silver halide photographic light-sensitive material which is capable of producing stable photographic properties with little fogging.

The above object of the present invention and other objects described below are to provide a silver halide photographic material having a light-sensitive emulsion layer containing silver iodobromide, in which component layers of the silver halide photographic material contain: Compounds selected from polyalkylene glycols having an alkylene oxide chain with a molecular weight of 300 or more and condensation products of alkylene oxide and organic compounds having active hydrogen (hereinafter referred to as polyalkylene oxide compounds).

) and a compound represented by the following general formula [1] and/or [■]. [Above general formula [1] and [■
], R1, R2, R3 and R4 each represent a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom, a carboxyl group, an alkoxycarbonyl group or a sulfo group, and at least one of R1, R2 and/or R3 , R4 is a carboxyl group, an alkoxycarbonyl group or a sulfo group.

] The present invention provides at least one polyalkylene oxide compound and the above general formula [1] and/or [■]
It is characterized by containing at least one of the compounds shown in combination in the component layer of the silver halide photographic light-sensitive material. At least one of each of these two types of compounds may be contained in the element layer, or at least one of each of these two types of compounds may be contained separately in two independent component layers. can be achieved.

A preferred embodiment of the present invention is to add the compound [A] into a photosensitive emulsion layer, and add the polyalkylene oxide compound into the emulsion layer and/or the non-photosensitive layer. One of the effects of the present invention is "high sensitivity", and in this specification, "high sensitivity" is defined as:
It is used as a word that has the meaning of high sensitivity and immediate increase in sensitivity.

The present invention will be explained in detail below. First, the above general formula [1
] and/or [■] (hereinafter referred to as compound [A]).

), the alkyl group of the lower alkyl group, alkoxy group, and alkoxycarbonyl group in the compound [A] represents a lower alkyl group having 1 to 4 carbon atoms, and each of the alkyl groups in the compound [A] It may be used in the form of water-soluble salts such as alkali metal salts and ammonium. A
These compounds [A] can be obtained by a known method, for example, by reacting a diamine compound with carbon disulfide, and can be obtained, for example, by the chemistry compound, heterocyclic compound, imizole, etc. And◆
Derivatives(]ChemistryOfHeter
OcyclollcCompOuImidazOlean
dDerivatives) VOl. l, P. 384 can be easily synthesized using the whistle method or similar methods.

Among the above compounds [A], 2-mercaptozimidazole-5-sulfonic acid is well known as a stabilizer for halogen emulsions [for example, E. J. Birr. ．． Z-W
issPhOt. ．． ? , NO. 46, P. lO3-12
6 (1953)] There is no suggestion whatsoever of suppressing the fogging of all halogenated agents that occurs when polyalkylene oid compounds are used.

7. Unexpectedly, the present inventors discovered that by introducing at least one syl group, alkoxycarbonyl group, or sulfur group into the mercaptoimidazole or 2-mercaptoimidazole nucleus, Silver halide emulsion produced by a polyalkylene oxide compound, especially using silver iodobromide as the silver halide,
It has been found that the formation of fog in the process can be significantly suppressed, and that it has the advantage of not being accompanied by desensitization.

The present invention is preferably applied to a highly sensitive X-ray photosensitive material that can reduce the initial amount of X-rays irradiated to the human body. Both the compound [A] according to the present invention and the polyalkylene oxide compound are well-known as materials for silver nogenide emulsions when used alone, but when they are used in combination, there are two different CJ could never have imagined that by using a specific compound form of any of the compounds, great benefits could be realized in photosensitive f using silver iodide.

Various polyalkylene oxide compounds can be used in the present invention, such as condensation products of polyalkylene glycols, aliphatic alcohols, aliphatic amines, or aliphatic amides with polyalkylene oxide. The total molecular weight of the polyalkylene oxide chain is It is sufficient to have an average molecular weight of at least 300 or more, preferably from 500 to 4,000, and the present invention is applicable even when the molecular weight is higher than that.

It can be used in the present invention.

Examples of these polyalkylene oxide compounds include, for example, Japanese Patent Publications No. 43-138, No. 47-874, No. 4
Publications such as No. 7-11116 and No. 40-378, or Japanese Unexamined Patent Publications No. 48-19213, No. 49-10722, and No. 4
No. 9-74929, No. 49-13072, No. 50-5
No. 7427, U.S. Pat. No. 51-321 Unagi, etc., or U.S. Pat.
No. 400532, No. 2423549, No. 2441
No. 389, No. 3017271, No. 3062647
Examples include compounds obtained by the methods described in the specifications of No. 2,312,553, No. 3,026,202, and British Patent No. 805,826. Typical specific examples thereof include the compounds listed below (however, the number in parentheses indicates the average molecular weight of the ethylene oxide chain). [
E-1] Polyethylene glycol (400) [E
-2] Polyethylene glycol (1500) [E
-3] Block condensate of polyethylene oxide and polypropylene oxide
(3000) [E-4] Condensate of polyethylene oxide and paratertiary butylphenol. (
1350) [E-5] Addition of polyethylene oxide and nonyl phenol formalin resin
Polymer (500) [E-6]
Condensate of polyethylene oxide and p-thiocresol (1500) [E-7] Addition polymer made by adding 1 mole of n-butyl mercaptan to a polymer of polyethylene oxide and polypropylene oxide (1000) [
E-8] Polyethylene oxide and lauryl
Condensate with alcohol (1250) [E-9]
Adduct of polyethylene oxide and β-monoethylthioethyl isocyanate
(600) [E-10] N-Laurilou N-
N-dipolyoxy diethylene-N-carboxymethyl-betaine (100
0) LCE-11) Condensate of N-tridecylamide and polyethylene oxide (350) [E
-12] Polyethylene oxide and octyl
Adduct with phenol-formalin resin
(800) [E-13] Condensate of polyethylene oxide and m-cresol (500) [E-14] Addition polymer of polyethylene oxide and polyglycidol with nonylphenolfulmarine resin
(500)
E-15] D-t-octylphenol and poly
Sodium sulfonic acid salt of adduct with ethylene oxide (650) In order to add and contain the compound [A] and the polyethylene oxide type compound used in the present invention in the silver halide photographic light-sensitive material, the silver halide photographic light-sensitive material Each may be added separately to at least one of the constituent layers of the material, or both may be added simultaneously in combination.

Further, each of them may be added separately to different layers (for example, a silver halide emulsion layer and a non-photosensitive layer such as a protective layer) in the component layers. Compound [A] and the polyethylene oxide compound can be added to the component layer by a known method. For example, when adding it to a silver halide emulsion layer, it may be added after being dissolved in water or an aqueous solvent (for example, about 1% by weight) after the second ripening is completed. The amount of compound [A] and polyethylene oxide compound used in the present invention varies depending on the type of silver halide emulsion used, purpose of use, development conditions, etc., but in general, the former compound [A] may be approximately in the range of 0.005 to 10y per mole of silver halide, preferably 0.
The object of the present invention can be achieved in 01-5y.

The latter polyalkylene oxide compound is preferably used in an amount of approximately 0.1 to 20 f per 1 e of coating liquid. The ratio of the addition amount of the polyalkylene oxide compound to the compound [A] is approximately 1 part by weight of the polyalkylene oxide compound to 0.0 parts by weight of the compound [A].
A range of 0.01 to 1 part is desirable. As the silver halide that can be applied to the silver halide photographic light-sensitive material of the present invention, silver iodobromide is used in order to obtain high sensitivity.

This silver iodobromide may be of any known type. The silver halide photographic light-sensitive material according to the present invention can be used for general black and white, for X-ray, for printing and copying, for inner/outer color, for monochrome or color diffusion transfer method, and for silver dye bleaching. It can be applied to silver halide photographic materials using silver iodobromide, but it is most suitable for X-ray use because of its high frequency range and fog suppressing effect. As the developer that can be applied to the silver halide photographic light-sensitive material according to the present invention, common developers such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-p-aminophenol or p-
A single additive such as phenylene diamine or a combination of two or more thereof is used, and other additives can be used in a conventional manner. Developers containing aldehyde hardeners can also be used in the silver halide photographic material according to the present invention, such as dialdehydes such as maleic dialdehyde or glutaraldehyde and their sodium bisulfite salts. It is also possible to use a developer known in the photographic field containing .

The silver halide emulsion used in the silver halide photographic material according to the present invention can be chemically sensitized in any type. That is, as a sulfur sensitization method, sensitization can be performed using sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, etc., and as a transmetal sensitization method, potassium chloroplatinate, ammonium chloropalladate, or Transmetallic salts such as ruthenium, rhodium, iridium, and platinum can also be used. These can be sensitized in combination with a sulfur sensitization method or in combination with rhodanammonium as an auxiliary agent. Furthermore, as a selenium sensitization method, for example, selenourea, N-N-dimethylselenourea,
US Patent No. 15 using N-dimethylselenourea etc.
Methods such as those disclosed in Japanese Patent Publication No. 74944, Japanese Patent Publication No. 3591385, Japanese Patent Publication No. 43-1, and Japanese Patent Publication No. 44-15748 can be employed, and as a reduction sensitization method, methods described in US Pat. The method using tin salts described in the specification, the method using polyamines described in U.S. Pat. Sensitization can also be carried out by the methods described in US Pat. No. 2,334,864, US Pat. No. 2,271,623, US Pat.

Furthermore, as a sensitization method using thioethers, methods described in US Pat. No. 3,021,215, British Patent No. 11,634, Japanese Patent Publication No. 11,116/1980, etc. can also be adopted.

The silver halide emulsion used in the present invention may be imparted with photosensitivity in a desired wavelength range using a sensitizing dye, and various sensitizing dyes can be used. One type or a combination of two or more types of sensitive dyes can be used.

Dyes that can be advantageously used in the present invention include methine dyes and styryl dyes such as cyanine, merocyanine, hemicyanine, rhodancyanine, oxol, and hemioxonol. Specifically, the sensitizing dyes described in the following patent specifications, publications, or literature are particularly effective for the present invention. That is, U.S. Patent No. 1,846,301
No. 1846302, No. 1939201, No. 1990507, No. 2072908, No. 21
No. 12140, No. 2165338, No. 22139
No. 95, No. 2269234, No. 2270378, No. 2442710, No. 2454629, No. 2493748, No. 2503776, No. 251
No. 9001, No. 2666761, No. 273914
9, the specifications of British Patent Nos. 2739964 and 2945763, British Patent Nos. 424559 and 43842.
吋, German Patent No. 450958, German Patent No. 50597, Specifications of German Patent No. 9290a, German Patent No. 2049967, Japanese Patent Publication No. 43-10251, Japanese Patent Publication No. 43-102♀
No. 43-13821, No. 44-32753, No. 45-27672, No. 45-27674, No. 45-
No. 27675, No. 46-18106, No. 46-181
No. 08, No. 47-8741, No. 47-23573,
Publications of No. 47-37443, Japanese Unexamined Patent Publication No. 48-897n
Publications etc. and Mass James (ML) S. Jam
es), The Theory of the Photographic
Process (TheOryOfthePhOtOg
rapicprOcess) 3rd edition (1965, The Macmillan Company, Themacmillan
Company) or Cyanine Dice and Related Compounds (by Hamer)
CyaninedyesandrelatedComp
Ounds), (196 details, Interscience Publishers, Interscience Pabll
(shers) etc. can be used. And among these, especially U.S. Patent No. 22139
No. 95, German Patent No. 2503776, German Patent No. 2945763, German Patent Nos. 92908 and 2049967, Japanese Patent Publication No. 13821/1986, Japanese Patent Publication No. 44-3275
Sensitizing dyes described in JP-A No. 3, No. 46-18101, No. 47-8741, No. 47-37443, and JP-A No. 48-8972 are effective in the present invention.

Typical examples of these pigments include 3,3''-di(3-sulfopropyl)selenacarbocyanine hydroxide, 5,5''-diphenyl-3●3
″-di(3-sulfopropyl)oxacyanine hydroxide, 3-aryl-5-[1-methyl-2(1H)piperidylidene]rhodanine, 3-(4-sulfobutyl)
-1''-ethyl-6''-methylselenium 2''-cyanine hydroxide, 1-hydroxyethyl-3-phenyl-5-[3-(3-sulfopropyl)-2-benzoxazolinidene] ethylidene-2-thiohydantoin Sodium salt, 5.5''-dichloro9-ethyl3●3'-
Di(3-sulfopropyl)oxacarbocyanine hydroxide, 5,5″-diphenyl-9-ethyl-3,3
- Di(3-sulfopropyl)oxacarbocyanine hydroxide, 5.5"-6.6"-tetrachlor 1.
1″-diethyl-3●3″-di(4-sulfobutyl)
-Benzimidazolocarbocyanine hydroxide sodium salt, 5.5″-di(butoxycarbonyl)-1.1
″-diethyl-3,3″-di(3-sulfopropyl)
Benzimidazolocarbocyanine hydroxide, 5.5
″-dichloro1●3″-diethyl-6″-methyl-3
-(4-Sulfobutyl)benzimidazolooxacarbocyanine hydroxide, 5,5"-dichloro9-ethyl-3,3"-(dicarboxyethyl)-thiacarbocyanine hydroxide, 5●5"-dichloro3●9 −
Diethyl-3″-(3-sulfopropyl)-thiacarbocyanine hydroxide, 5,5″-dimethyl-9-ethyl-3●35-di(3-sulfopropyl)-thiacarbocyanine hydroxide, 9-ethyl-3●3 ″-di(3-sulfopropyl)-4・5・4″・5″-dibenzothiacarbocyanine hydroxide, 9-ethyl-3・
3″-G(3-sulfopropyl)-5●6●5″・6
''-dipenzoxacarbocyanine hydroxide, etc. The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention may be used as a stabilizer and a fog suppressant, for example, U.S. Pat. No. 2,444,607, Same No. 271606, Same No. 3512982, Same No. 334
2596, German Patent No. 118938, German Patent No. 2058
Specifications of No. 626 and No. 211841, Special Publication No. 1973
No.-4133, No. 39-2825, JP-A-50-22
626 and No. 50-25218 may be applied, and particularly preferred compounds include 5●6-trimethylene-7.
-Hydroxy-S-triazolo(1,5-a)pyrimidine, 5,6-titramethylene-7-hydroxy-S-triazolo(1●5-a)pyrimidine, 5-methyl-7-
Hydroxy-S-triazolo(1,5-a)pyrimidine, 7-hydroxy-S-triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate, etc.) , mercaptans (e.g. 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, etc.), benztriazoles (e.g. 5-promnobenztriazole, 4-methylbenztriazole, etc.), benzimidazoles (e.g. 6-nitrobenztriazole, etc.) imidazole, etc.).

The silver halide photosensitive material according to the present invention uses a photographic hardening agent commonly used in its coating solution, such as an apaldehyde hardener or an aziridine hardener (for example, PB Report, 19921, U.S. Pat. No. 2,950,197, U.S. Pat. No. 2,964,404). No. 2
No. 983611, No. 3271175, Japanese Patent Publications No. 46-40898, and Japanese Patent Application Laid-open No. 91315-1983), isoxazole type (for example, as described in US Pat. No. 331,609) ), epoxy systems (for example, those described in the specifications of U.S. Patent No. 3,047,394, West German Patent No. 1,085,663, British Patent No. 1,033,518, and Japanese Patent Publication No. 48-35495),
Vinyl sulfone type (e.g. PB Report 19920.
West German Patent No. 110094? , UK Patent No. 1251091
No., Patent Application No. 45-54236, No. 48-110996
acryloyl type (for example, those described in the specifications of Japanese Patent Application No. 48-27949 and U.S. Patent No. 36407), Carbodiimide type (for example, US Pat.
5 and Japanese Patent Application No. 49-15095), maleimide-based hardeners, acetylene-based hardeners, methanesulfonic acid ester-based hardeners, triazine-based hardeners, and polymer hardeners. In addition, as a thickening agent, for example, U.S. Pat.
167410, Belgian Patent No. 558143, polyols as gelatin plasticizers (for example, U.S. Pat. Publication), and US Patent No. 76 as latex.
69, the specifications of French Patent No. 1395544, those described in Japanese Patent Publication No. 48-43125, and those described in British Patent No. 12219 (to) as matting agents can be used. . Desired coating aids can be used in the constituent layers of the silver halide photographic material according to the present invention, such as saponin or sulfosuccinic acid surfactants such as those described in British Patent No. 5485.
3. Those described in the specifications of Japanese Patent Application No. 47-89634, or as anionic surfactants, for example,
-13166 publication, U.S. Patent No. 3514293, French Patent No. 2025688 specifications, Japanese Patent Publication No. 43
Those described in Japanese Patent No.-10247 can be used.

The silver halide photographic material according to the present invention includes gelatin, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, For example, British Patent No. 523611, German Patent No. 2255711, German Patent No. 204668? , and the specifications of US Pat. No. 3,341,33, etc. may be used.

Further, as gelatin derivatives, for example, US Pat.
Phenylcarbamyl gelatin, acylated gelatin as described in No. 14928 and No. 2525753,
Phthalated gelatin or polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester described in U.S. Pat. These hydrophilic colloids can be used in other photographic materials, such as filter layers, protective layers, interlayers, etc. that contain or do not contain silver halide. It may also be used in component layers.
When the present invention is applied to a color photosensitive material, various types of couplers can be used. For example, an open-chain ketomethylene type coupler can be used as a yellow coupler, and a pyrazolone type coupler can be used as a magenta coupler. Compounds such as pyrazolotriazole, pyrazolinobenzimidazole, and indazolone can be used.

Furthermore, as the cyan coupler, phenol-based, naphthol-based, and other compounds can be used. Furthermore, the photographic emulsion in this case may be a strong lard magenta coupler, a strong lard cyan coupler, a DIR coupler, a BAR coupler, a weiss coupler, or a repeating coupler. Tinupin (trade name, Ciba Geigy) described in No. 1763, No. 48-4157, etc. may be used, as well as fluorescent brighteners, image stabilizers, antioxidants, lubricants, and metal ions. Various photographic additives such as blocking agents and emulsifying dispersants can be used.The silver halide photographic light-sensitive material according to the present invention includes a filter layer and an anti-halation layer as layers other than the silver halide emulsion layer (photosensitive layer). Auxiliary layers such as a layer, a protective layer, an intermediate layer, and a subbing layer may be provided, or erasure prevention may be provided.

Supports used include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, Various materials such as styrene film can be used, and each of these branch carriers is appropriately selected depending on the purpose of use of the silver oxide photographic light-sensitive material. Hereinafter, the present invention will be illustrated by examples, but the embodiments of the present invention are not limited thereby.

Example 1 Immediately before the completion of the second ripening of a highly sensitive silver iodobromide gelatin emulsion containing 1.5 mol % of silver iodide, the above exemplary compound [E-4] was added to silver halide 1 as a polyalkylene oxide sensitizer.
It was added as an aqueous solution at a concentration of 0.5 Da per mole.

After adding a tetrazaindene compound as a fog stabilizer to this emulsion, it is divided into 7 parts, and a coating aid and a hardening agent are added to one part to give a dry film thickness of 10μ on a triacetate film base. This was used as a comparison sample (sample number 1). The exemplified compounds [A-1] and [A-4] were added to the remaining 6 parts of the emulsion as compound [A].
and [A-10] each at 0 per mole of silver halide.
．． After adding 0.05y and 0.2y, 6 types of samples shown in Table 1 below (sample number 2
, 3, 4, 5, 6 and 7) were prepared.

Next, these test and comparative samples were exposed to white light according to the JIS method using a sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd., Model KS-1), and then developed using an automatic processor (developing → fixing → washing with water). (1 drying). However, the developing conditions were development at 40° C. for 30 seconds, and the developer formulation was as follows. [Developer formulation] Hydroquinone 100y1-
Phenyl-3-pyrazolidone 0.4y anhydrous sodium sulfite 70y sodium carbonate (
monohydrate) 20y boric anhydride
1q sodium hydroxide
5y5-methylbenzotriazole 0
．． 05g potassium bromide 5y
Glutaraldehyde bisulfite 15g glacial acetic acid
Add 8y water and 1e
Finish it.

About the samples obtained in this way and comparative samples J
Sensitometry was performed using the IS method to measure sensitivity and fog.

The results are shown in Table 1. Note that the sensitivity shown in the table is expressed as a relative value with respect to the sensitivity of the comparative sample as 100. As is clear from Table 1, fog can be effectively suppressed by adding compound [A] to the silver halide photographic light-sensitive material sensitized with a polyalkylene oxide compound. Example 2 A silver iodobromide gelatin emulsion for X-rays containing 2 mol% of silver iodide was added with a tetrazaindene compound as a fog stabilizer after the second ripening.
After adding an aldehyde compound as a hardening agent and a coating aid, the mixture was divided into 7 parts, and 1 part was coated onto a polyethylene terephthalate film base to give a dry film thickness of 10 μm.

On the silver halide emulsion layer thus obtained, a 3% gelatin aqueous solution containing 0.1 y of the above-mentioned exemplified compound [E-5] per 1 y of gelatin as a polyalkylene oxide antistatic agent was applied to a dry film thickness. It was coated to a thickness of 2 μm, and this was used as a comparison sample (sample number 8).

The exemplified compounds [A-2], [A-7] and [A-12] were added as compound [A] to the remaining 6 parts of the emulsion.
0.05 per mole of silver halide, as shown in the table.
g and 0.2y were added, and six types of samples (sample numbers 9, 10111, 1
2, 13 and 14) were prepared.

The samples obtained in this way and comparative samples were tested at a tube voltage of 6
0KVp1 tube current 200TL. X-ray sensitometry was carried out through X-ray fluorescent intensifying paper (manufactured by Tokyo Shibaura Electric Co., Ltd.) having medium sensitivity (A) and an aluminum step wedge. Each of these samples was treated with the following developer solution.
℃ for 4 minutes, followed by fixing, washing with water, and drying in the usual manner. Table 2 shows the sensitivity and fog measurement results.
However, the sensitivity is expressed as a relative value with the sensitivity of the comparative sample as 100. [Developer prescription] Hydroquinone
10 da 1-phenyl-3-pyrazolidone
0.3q anhydrous sodium sulfite 50
y Sodium carbonate (monohydrate) 20f Boric anhydride 1y Potassium bromide
Add 5y of water to make 1f.

As is clear from Table 2, the addition of compound [A] is extremely effective in suppressing fog during high-temperature development of silver halide photographic materials containing a polyalkylene oxide compound as an antistatic agent in the protective layer. I understand that there is something.

Example 3 A silver iodobromide gelatin emulsion for X-rays containing 2 mol% of silver iodide was sensitized with gold, and after adding a tetrazaindene compound as a fog stabilizer, it was divided into 16 parts, of which After adding a hardener and a coating aid to 6 parts of emulsion, a dry film thickness of 10 μm was formed on a polyethylene terephthalate film.
It was applied so that

A 3% gelatin aqueous solution was coated on part of the emulsion layer of this coated sample to prepare a comparative sample (sample number 15). Further, on the remaining 5 parts of the emulsion layer of the coated sample, 5 types of polyalkylene oxide compounds shown in Table 3 below were added to 11 parts of gelatin, respectively. Apply an aqueous gelatin solution containing 0.1y per layer.5
Types of comparison samples (sample number 1den 1λ22, 25 and 2
8) was produced. After adding 0.1y of the two types of compounds [A] shown in Table 3 to the remaining w part of the emulsion, 0.1y per mole of silver halide was added, and 1% was added in the same manner as the comparative sample.
A 3% gelatin aqueous solution containing 0.1 y of the five types of polyalkylene oxide compounds per 1 y of gelatin was placed on the emulsion layer of these coated samples, as shown in Table 3. 10 types of samples (sample numbers 17, 18, 20, 21, 2 in 2 ton 2 den 27, 2
9 and 30) were prepared. These single samples were exposed and developed in the same manner as in Example 1, and the results are shown in Table 3. However, the sensitivity is expressed as a relative value with Comparative Sample 15 as 100. As is clear from Table 3, it can be seen that fog caused by polyalkylene oxide compounds can be effectively suppressed by adding compound [A].

Example 4 The following layers were sequentially formed on a support made of cellulose triacetate film from the support side.

Layer 1... Anti-halation layer Layer 2... Gelatin intermediate layer 3... Cyanine dissolved in Tory-0-cresyl phosphate and dispersed in an aqueous gelatin solution. 1-Hydroxy N-(δ-(2・4) as a coupler
Red-sensitive silver halide enzyme containing 1.4yI -t-amylphenoxy)butyl)-2-naphthamide
Latin emulsion layer 4... Gelatin intermediate layer 5... 1-(2. 4.6-trichlorophenyl)-3-(3-[α-(2.4-di-t-amylphenoxy)-acetamide]benzamide)
-5-pyrazolone and 1-(2,4,6-trichlorophenyl)-3-(3-[α-(2,4-di-t-amylphenoxy)-acetamido]benzamide)-4-(4-methoxyphenyl) Azo) - 5
- Green-sensitive silver halide gelatin emulsion layer 6 containing 1.8y1d of pyrazolone... Gelatin intermediate layer 7... Filter layer 8 containing yellow colloidal silver...・α-(4-nitrophenoxy)-α-pivalyl 5 as a yellow coupler dissolved in dibutyl phthalate and dispersed in an aqueous gelatin solution.
-[γ-(2,4-di-t-amylphenoxy)butyramide 2-chloroacetanilide at 2.4fI
B Containing blue-sensitive silver halide gelatin emulsion layer Layer 9... Gelatin protective layer However, each of the above layer-3, layer-5 and layer-8 emulsion layers is a high-sensitivity iodobromide layer for color use. The emulsion consists of a silver emulsion (containing 5 mol% silver iodide), and exemplified compounds [E-6] and [E-9] are added to each of these three layers as a sensitizer just before the end of the second ripening. It was added in an amount of 0.5y per mole of silveride.

In addition, tetrazaindene compounds (4
-Hydroxy-6-methyl-1●3.C.7-tetrazaindene) was also added in a predetermined amount. The above film was used as a comparative sample (sample numbers 31 and 35), and the exemplified compound [A-
5], [A-6], [A-9], [A-10], [A-
Samples according to the present invention (sample numbers 32, 33. Otori 3 Saka 37 and O) were prepared exactly the same as the above comparative samples except that 11) and [A-12] were added as shown in Table 4 below. was created.

Next, exposure was carried out according to the method of Example 1, and then development was carried out at 38°C for 3 minutes and 15 seconds using a color developing solution having the following composition.

[Color developer composition]

4-amino-3-methyl-N-ethyl(β-hydroxyethyl)-aniline sulfate 4.8y anhydrous sodium sulfite 0.14y hydroxylamine (1-2 sulfate) 1.98 sulfuric acid
0.74mt7 anhydrous potassium carbonate
28.85y anhydrous potassium bicarbonate
3.46V anhydrous potassium sulfite 5.
10 da potassium bromide 1.16
y Sodium chloride 0.14f Funitrilotriacetic acid (monohydrate) 1.20f Potassium hydroxide 1.48y Add water to make 1e.

Next, the procedure of stopping, fixing, washing and bleaching was carried out in the usual manner, followed by two washes under running water and drying, followed by use as a measurement sample.

Separately, as a film storage test, samples were prepared which were left under high temperature and high humidity as shown in Table 4 below, and were subjected to color development treatment in the same manner as above to be used as measurement samples.

Sensitometry was performed on each of the obtained samples according to the JIS method.

The results are shown in Table 4 below. The sensitivity values in the table are
The respective sensitivities to blue, green, and red light of the natural sample that does not contain the compound [A] according to the present invention are 1
It is expressed as relative sensitivity when set to 00. As is clear from Table 4, it can be seen that the samples according to the present invention have stable photographic properties even under severe storage conditions.

Example 5 A high-sensitivity X-ray silver iodobromide gelatin emulsion [A] containing 2.5 mol% silver iodide was enriched with gold and sulfur, and a tetrazaindene compound, a hard After adding an aldehyde compound as a film agent and a coating aid, the mixture was divided into 4 parts, and the exemplified compound [A-
7] was added and coated on a polyethylene terephthalate film base to a dry film thickness of 10 μm.

On the other hand, silver chlorobromide emulsion [B] whose silver halide composition contains 70 mol% silver chloride and 1.0 mol% silver iodide,
Silver chloroiodobromide emulsion [C] containing 75 mol % of silver chloride was also coated in the same manner as for emulsion [A].

On the silver halide emulsion layer thus obtained, a fifth
As shown in the table, polyethylene oxide compound [E-5]
A 3% gelatin aqueous solution containing 0.1 y of gelatin per y of gelatin was coated so that the dry film thickness was 2 μm.

The samples thus obtained were exposed and developed in the same manner as in Example 1, and the results are shown in Table 5.

However, the sensitivity is shown as a relative value with Comparative Sample 39 as 100. As is clear from Table 5, the effects of the present invention of high sensitivity and low fog are observed only in silver iodobromide emulsions, and not in silver chlorobromide emulsions or silver chloroiodobromide emulsions.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic light-sensitive material having a light-sensitive emulsion layer containing silver iodobromide, a polyalkylene glycol having an alkylene oxide chain having a molecular weight of 300 or more and an organic compound having an alkylene oxide and active hydrogen. A silver halide photographic photosensitive material containing a combination of at least one compound selected from condensation products with other compounds and a compound represented by the following general formula [I] and/or [II] material. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_
1, R_2, R_3, and R_4 each represent a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, or a sulfo group, and at least one of R_1, R_2 and/or R_3, R_4 At least one of them is a carboxyl group, an alkoxycarbonyl group, or a sulfo group. ]