JPS62169149A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high contrast image having sensitivity and high maximum density by holding photosensitive silver halide particles, metallic salt particles having internal fog and a specified polyol on a support. CONSTITUTION:Photosensitive silver halide particles, metallic salt particles having internal fog and a polyol having >=40 deg.C m.p. and at least two hydroxyl groups in the molecule are held on a support to obtain a silver halide photographic sensitive material having small dependency on processing conditions and giving a high quality image by processing at a high temp. The sensitive material also causes little change in sensitivity and gradient and produces a significant effect even during processing at a low temp., usually at about 20 deg.C for 2-20min development time. The polyol having >=40 deg.C m.p. and at least tow hydroxyl groups in the molecule is a 2-20C alcohol having 2-12 hydroxyl groups not conjugated with a conjugate chain in the molecule. The preferred m.p. of the polyol is 50-300 deg.C.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel silver halide photographic material, and more particularly, to a silver halide photographic material that provides high sensitivity, high contrast, and high maximum density images. It's about materials.

[Conventional technology]

Increasing the sensitivity of the film is important to reduce the use of 1fffffi. For example, in X-ray film,
It is also important for reducing radiation exposure.

One way to increase the sensitivity of a film is to reduce the hardness of the film layer made of gelatin or the like. However, this method is not preferable because it deteriorates the graininess of the developed image and deteriorates the physical properties of the film.

JP-A-57-89749 discloses thioethers (
For example, C6HI 30cOcHzcHtscfl□CH
A method is disclosed in which a development accelerator such as zSC1hC1hOCOCJI+ 3) or a nitrogen-containing cyclic compound having a thioketone group is added to a silver halide emulsion or a developer. However, if this method is used to increase sensitivity, graininess will deteriorate, and if added to a silver halide emulsion, fog will increase during storage, which is not preferable.

Increasing the grain size of the silver halide emulsion also increases sensitivity, but to obtain both high sensitivity and the required maximum image density, more silver salt must be contained per unit area of the film. It is also undesirable because it causes deterioration of graininess and reduction of covering power (Japanese Patent Application Laid-Open No. 59-148).
Publication No. 051).

As an attempt to improve covering power while maintaining high sensitivity, a technique for adding various polymers to high-sensitivity coarse grain silver halide emulsions was published in British Patent No. 1,048,0.
No. 57, No. 1,039,471, U.S. Patent No. 3,0
No. 43,697 and No. 3,446,618. All of these have the effect of increasing the covering power to some extent, but are not sufficient, and furthermore, they weaken the strength of the coating film, which is not preferable.

Furthermore, this method is not preferable because fog changes significantly over time and uneven development is likely to occur depending on the development processing method.

Further, JP-A-52-42725 and the like describe a so-called amplifier technique in which a black coupler imagewise contains an organic substance that develops color. However, this method is not preferable because the organic substances contained therein are unstable, so deterioration over time is large, and depending on the development method, uneven development is likely to occur.

On the other hand, U.S. Patent No. 2,996,382 and U.S. Patent No. 3.1
No. 78.282 describes the use of a silver halide photographic material in which surface latent image type silver halide coarse particles and silver halide fine particles having fog nuclei inside are supported in the same layer or in an adjacent layer. It is described that photographic images with high sensitivity, high contrast and high covering power can be obtained.

However, this method has the problem that fog is likely to occur during development.

Furthermore, in this method, sensitivity and gradation changes are large during high-temperature processing (processing at a temperature of 30° C. or higher), and stable photographic performance cannot be obtained. As a technique for improving this problem, JP-A-60-166944 describes the use of a mesoionic triazolium compound, but this compound alone is not preferred because it causes desensitization.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a silver halide photographic material that provides images with high sensitivity, high contrast, and high maximum density.

Another object of the present invention is to suppress the occurrence of fog and extremely increased changes in sensitivity and gradation, particularly during high-temperature rapid processing, and to suppress changes in sensitivity and gradation due to temperature variations at high temperatures. The goal is to reduce it.

That is, an object of the present invention is to provide a silver halide photographic material that always provides stable photographic performance.

[Structure and operation of the invention]

The above object of the present invention is to provide photosensitive silver halide grains on a support, metal salt grains having internal fog and a melting point of 4.
This can be achieved by using a silver halide photographic material that has a temperature of 0° C. or higher and contains a polyhydric alcohol having at least two hydroxyl groups in its molecule.

Furthermore, according to the present invention, not only can high-quality images and silver halide photographic materials with low processing dependence be obtained by high-temperature processing, but also low-temperature processing (generally around 20°C, development time of 2 to
Even after 20 minutes), it was confirmed that the change in sensitivity and gradation was small and that excellent effects were exhibited.

The polyhydric alcohol having a melting point of 40°C or more and having at least two or more hydroxyl groups in the molecule used in the present invention has 2 to 12 hydroxyl groups in the molecule and 2 to 20 carbon atoms. It is an alcohol in which the hydroxyl groups are not conjugated with each other through a conjugated chain, that is, the oxidized form cannot be written, and the melting point is 50°C or higher, and the melting point is 300°C or higher.
℃ or less is preferable.

Specific examples will be given below in numbers 1 to 50, but the present invention is not limited to these specific examples.

5,2,5-hexanediol 43-447
, 1,6-hexanediol 428,1
,8-octanediol 609.1
．． 9-nonanediol 4510,
LIO-decanediol 72-741
1,1.11-undecanediol 62-62
．． 512, 1,12-dodecanediol 79
~79.513, 1,13-tridecanediol
76.4-76.614, 1,14-tetradecanediol 83-8515, 1,12-octadecanediol 66-6716, 1.18-octadecanediol 96-9818, trans-2,
5-dimethyl-3-hexene-2,5-diol
7719.2-Butyne-1,4-diol
5520, 2,5-dimethyl-3-hexyne-2,5-diol 9522
, 2,6-octadiyne-1,8-diol
88.5-89.524, 2.3.4-hexanetriol approx. 4727, pentamethylglycerin 116-11731, erythritol 12632, D-
1-Leisoto 8833, L
-1-Rayt 88~893
4, rac-) Raitt
7235, Pentaerythritol 260
~26536, 1,2,3.4-pentanetetrol
10637, 2.3,4.5-hexanetetrol 16239, 1,2.5.6-hexanetetrol 9540, 1.3,4.5-hexanetetrol 8842.3-hexene-1
,2,5,6-tetrol 8
0-8243.3-hexyne-1,2,5,6-tetrol 113-114.544, adonitol 10245, D-
arabitol 10246, L-arabitol 10247, rac
~arabitol 10548, xylitol 93-94,549, mannitol 16450, dulcitol 188.5-189 There is no particular restriction on the amount of the above compounds 1-50, but halogenated i
The amount is 1 g to 100 g, preferably 5 to 50 g per mole of barb. The above compounds Nos. 1 to 50 are added to the layer adjacent to the silver halide emulsion layer. Preferably, it can be added to at least one or both of a photosensitive silver halide emulsion and a metal salt emulsion having fog nuclei inside, or to a mixed system of a silver halide emulsion and a metal salt emulsion having fog nuclei inside. The timing of addition is arbitrary, but it should be added between the end of chemical aggravation and during application. As for the addition method, it may be directly dispersed in a hydrophilic colloid, or it may be added after being dissolved in an organic solvent such as methanol or acetone.

In the present invention, "photosensitive" means that the sensitivity of the photosensitive silver halide grains is higher than the sensitivity of the metal salt grains covered inside. More specifically, it means having a sensitivity that is 10 times or more, more preferably 100 times or more, the sensitivity of the internal metal salt particle.

The sensitivity here is defined in the same way as the sensitivity shown below.

As the photosensitive silver halide emulsion, a conventional silver halide emulsion such as a surface latent image type emulsion is used.

Here, the surface latent image type silver halide emulsion is 1 to 1/1
After 00 seconds of exposure, when developing using the surface development (A) method and internal development (B) method shown below, the sensitivity obtained with surface development (A) is higher than the sensitivity obtained with internal development (B). The sensitivity of the former is preferably twice that of the latter. Here, sensitivity is defined as follows.

Eh S is sensitivity, Eh is maximum density (Dmax) and minimum density (D
density 'A (Dmax + Dm
Indicates the amount of exposure required to obtain in).

[Surface development (A)]

Developed for 10 minutes at a temperature of 20°C in a developer having the following formulation.

[Internal development (B)]

Red blood salt 3g/l and phenosafnin 0.0126g/
The sample is treated in a bleaching solution containing 20° C. for 10 minutes at about 20° C., then washed with water for 10 minutes, and then developed in a developer having the following formulation at 20° C. for 10 minutes.

Specifically, as the surface latent image type silver halide, silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide can be used. Here, the content of silver iodide is 0.1 to 3
It is preferably in the range of 0 mol %, particularly 0.5 to 10 mol %. The average grain size is preferably larger than that of a silver halide emulsion having internal fog nuclei, particularly 0.
It is preferable that it is 6 μm or more. The particle size distribution may be narrow or wide. Silver halide grains in emulsions have regular (re) shapes such as cubes, octahedrons, and dodecahedrons.
It may have a gular crystal shape, or it may have an irregular (irregular) crystal shape such as spherical, plate-like, potato-like, etc.
It may have a crystalline form (ular) or a composite form of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms. Further, tabular grains having a grain size of three times or more the grain thickness are preferably used in the present invention.

The photographic emulsion used in the present invention is P, Glafkides.
Author, Hemi Engineering Physique Photography (C
himie et Physique Photogr
aphique, published by Pau1Monte1, 196
7), G.F. Duffin, Photo-gra
phic emulsion chemistry),
The Focal Press, 1966),
Making and Coating Photographic Ink Emulsions by V, L, Zelikman et al.
photo-graphic emulsion, Th
e Focal Press, 1964). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping p/Ig constant in the liquid phase in which silver halide is produced, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The emulsion used in the present invention is usually stripped of soluble salts after precipitation or physical ripening, and the long-known Nodel water washing method, which involves gelling gelatin, may be used as a means for this purpose. Also, inorganic salts consisting of polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated A sedimentation method (flocculation) using gelatin, etc.) may also be used. Note that the process of removing soluble salts may be omitted.

Photosensitive silver halide emulsions are made without chemical sensitization.
Although so-called "primitive" emulsions can be used as they are, they are usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
The book by Elikman et al. or Il, Fr1ese
rfi de grundlagen der fotografisien brotzese mid zilberhalogeninieden (D
ieGrundlagen der Photogra
phischen Prozesse mitSilb
Erhalogeniden, Akademisch
e Verlagsgesell-schaft, 1
968) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur aggravating agent, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat. No. 1,574,944;
No. 2,410,689, No. 2.278.947, 2,7
No. 28.668 and No. 3,656,955. As the reduction aggravating agent, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof can be found in U.S. Pat. ,2,5
18.698, 2.983,609, 2,983,
No. 610, No. 2,694.637. For noble metal sensitization, in addition to total complex salts, platinum, iridium,
Complex salts of metals in group I of the periodic table, such as palladium, can be used; specific examples thereof include U.S. Pat. No. 2,399,083;
2.448,060, British Patent No. 618,061, etc.

Next, as metal salt particles having fog nuclei inside to be used in the silver halide photographic light-sensitive material of the present invention, JP-A-57-1
38633, 57-140317, 57-1542
There are photosensitive halogenated W4 grains described in No. 33 and thallium (I) compounds (eg, TlBr, TIN, etc.), but silver halide grains are preferred.

Further, the metal salt particles having fog nuclei inside may be stabilized using a compound having a mercapto functional group.

Compounds having a mercapto functional group include, for example, heterocyclic nitrogen compounds having a mercapto functional group, in which the mercapto group is bonded to a carbon atom at the α-position relative to the nitrogen atom of the heterocyclic ring; , tetrazaindenes with at least one mercapto function, purines with at least one mercapto function, triazaindenes with at least one mercapto function,
Examples include pentazaindenes having at least one mercapto functional group.

In the silver halide photographic light-sensitive material of the present invention, high sensitivity, high contrast, and increased covering power can be achieved by using a metal salt emulsion with internal fogging together with a high-iodine photosensitive silver iodobromide emulsion. I can do it.

Here, it is preferable that the sensitivity of the internal fogged metal salt emulsion is lower than the sensitivity of the photosensitive silver halide emulsion. More specifically, the sensitivity of the internally fogged metal salt emulsion is preferably 10 times or less, more preferably 100 times or less (relative to the light-sensitive silver halide emulsion).

For example, as a silver halide emulsion having internal fog nuclei used in the silver halide photographic light-sensitive material of the present invention, a test piece coated on a transparent support at a silver content of 2 g/m is not exposed. When developed with D-19 (a developer specified by Eastman Kodak Company) at 35°C for 2 minutes, 0.
A transmission fog density of 5 or less (excluding the density of the support itself) was obtained, and the same test piece was developed for 2 minutes at 35°C with a developer containing 0.5 g/l of potassium iodide in To19 without exposing it to light. An emulsion is used which gives a transmission fog density (excluding the density of the support itself) of 1.0 or more when this is done.

Silver halide emulsions having fog nuclei inside can be prepared by various methods. Light or
There are methods such as irradiating with radiation, chemically creating fog nuclei using a reducing agent, gold compound or sulfur-containing compound, and producing an emulsion under conditions of low 9Ag and high pH. To create fog nuclei only on the inside, there is a method in which both the interior and surface of the silver halide grain are fogged by the above method, and then the fog nuclei on the surface are bleached with a red blood salt solution, but it is more preferable. The method is to first prepare a core emulsion having fog nuclei by a low p/Ig, high pH method or a chemical fogging method, and then cover the core emulsion with a shell emulsion. For the preparation method of this core-shell emulsion, reference can be made to, for example, the description in US Pat. No. 3,206,313.

The metal salt emulsion having fog nuclei inside has an average grain size smaller than that of the silver halide emulsion, and has a grain size of 1.0 to 1.0.
Preferably, those with an average particle size of 0.05 μm;
Those with an average particle size of 0.6 to 0.1 .mu.m are more preferred, and those below 0.5 .mu.m are particularly preferred and give good results.

The internally fogged silver halide emulsion may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, and the like.

The content ratio of the photosensitive silver halide grains and the internally capped metal salt particles in the silver halide photographic material of the present invention is determined by the emulsion type used (for example, halogen composition), the type of photosensitive material used, Although it can be changed depending on the purpose, the contrast of the emulsion used, etc., it is preferably 10 (hl to 1 = 100, especially lO: 1 to 1
:10 is preferable. In addition, the total amount of coated silver is 0.
．． 5 to 10 g/rrf is preferred.

Various hydrophilic colloids can be used as binders in the silver halide photographic material of the present invention.

Colloids used for this purpose include hydrophilic colloids commonly used in the photographic field, such as gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, etc. be able to. Along with the hydrophilic colloids, hydrophobic colloids such as dispersed polymerized vinyl compounds, especially those which increase the dimensional stability of silver halide photographic materials, can be included. Suitable compounds of this type include water-insoluble polymers made by polymerizing vinylic monomers such as alkyl acrylates or alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles,
benzimidazoles (especially nitro- or halogen-substituted), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-5
-mercaptotetrazole), mercaptopyridines The above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a dicarboxyl group or a sulfone group, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy substituted 1, 3, 3a
,? A number of compounds known as stabilizers can be added, such as tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is K. Mees, The Theory Turns to the Photographic Ink Process (Th
e Theory of the Photography
hicProcess.

(3rd edition, 1966), citing the original literature.

For more detailed examples of these and how to use them, see, for example, U.S. Pat. Nos. 3,954,474 and 3,98
Reference may be made to the specifications of No. 2,947 and No. 4,021,248 or Japanese Patent Publication No. 52-28660.

Several embodiments are conceivable regarding the layer structure of the silver halide photographic light-sensitive material according to the present invention.

Representative ones are shown below (11 to (5)).

(11) Photosensitive silver halide grains, metal salt grains having fog nuclei inside, and polyhydric alcohols having a melting point of 40°C or higher and having at least two or more hydroxyl groups in the molecule (hereinafter simply referred to as polyhydric alcohols). (2) First, an emulsion layer containing metal salt particles having fog nuclei inside is coated on the support. Further, an emulsion layer containing photosensitive silver halide grains and a polyhydric alcohol is coated thereon. (3) First, photosensitive silver halide grains and metal salt particles having fog nuclei inside are coated with the same coating composition. (4) photosensitive silver halide grains, and an emulsion layer containing the photosensitive silver halide grains; A coating composition (emulsion) containing metal salt particles having fog nuclei and a polyhydric alcohol is coated on a support, and further thereon, photosensitive silver halide grains and a polyhydric alcohol having fog nuclei therein are added. A configuration in which an emulsion containing a metal salt particle emulsion with a composition different from that of the lower layer is coated. For example, a structure in which a gelatin coating layer containing .

In the silver halide photographic material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be hardened with any suitable hardener.

These hardening agents include mucochloric acid, mucobromic acid,
Mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dimethylol urea, trimethylolmelamine, glyoxal, momemethylglyoxal,
2,3-dihydroxy-1°4-dioxane, 2,3-
Aldehyde compounds such as dihydroxy-5-methyl-1,4-dioxane, succinic aldehyde, 2゜5-dimethoxytetrahydrofuran, glutaraldehyde Nidivinyl sulfone, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro -3-triazine, 1,3.5-)lyacryloyl-hexahydro-5-)lyazine, 1,3,5-)rivinylsulfonyl-hexahydro-5-)lyazinebis(vinylsulfonylmethyl)ether, 1. Active vinyl compounds such as 3-bis(vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane = 2.4-dichloro-6-hydroxy-5-)riazine sodium salt, 2.4 -dichloro-6-medoxys-
) riazine, 2.4-dichloro-6-(4-sulfoanilino)-s-triazine sodium salt, 2.4-dichloro-6-(2-sulfoethylamino)-S-) riazine, N,N'- Active halogen compounds such as bis(2-chloroethylcarbamyl)piperazine: bis(2,3-
epoxypropyl) methylpropylammonium p-
) luenesulfonate, 1.4-bis(2',3'-epoxypropyloxy)butane, 1.3.5-triglycidyl isocyanurate, 1.3-diglycidyl-5-
Epoxy compounds such as (T-acetoxy-β-oxypropyl)isocyanurate: 2.4.6-)liethyleneimino S-triazine, 1.6-hexamethylene-N,N'-bisethyleneurea, bis- Ethyleneimine compounds such as β-ethyleneiminoethylthioether, 1°2-di(methanesulfonoxy)ethane, 1.
Methanesulfonic acid ester compounds such as 4-(methanesulfonoxy)butane and 1,5-di(methanesulfonoxy)pentane; furthermore, carbodiimide compounds,
Examples include isoxazole compounds and inorganic compounds such as chromium aerobane.

The photographic emulsion layer or other constituent layers of the silver halide photographic light-sensitive material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration,
Surfactants other than those of the present invention may be included for various purposes such as high contrast, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols alkylamides or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as sugar alkyl esters,
Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurate sulfosuccinate, sulfoalkyl polyoxy Carboxy groups such as ethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, and phosphate ester groups; amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, and amine oxides; Cationic surfactants such as surfactants, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles. Agents can be used.

The silver halide photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Further, the silver halide photographic light-sensitive material of the present invention includes U.S. Pat. No. 3,411,911 and U.S. Pat.
The alkyl acrylate latex described in No. 912, Japanese Patent Publication No. 45-5331, etc. can be used as a surplus.

Other additives may be added to the silver halide emulsion, especially those useful in photographic emulsions, such as lubricants, sensitizers, light-absorbing dyes, and the like.

In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, such as viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a core with a ketomethylene structure, such as a birapurin-5-one core, a thiohydantoin core, and a 2-thioxazolidine-2 core.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion. About 1, OXl0-' to about 5X10-' mole of sensitizing dye per mole of silver halide, especially halogenated! I! Approximately 4 sensitizing dyes per mole
It is preferred to use a concentration of between X10-' and 2X10-' molar.

The silver halide emulsion of the present invention may contain a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) that reacts with the oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. good. The coupler is preferably a non-diffusible coupler having a hydrophobic group called ballast M in its molecule. The coupler has 4 equivalents or 2 equivalents for the i ion.
Either equivalence is acceptable. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The coupler may be such that the product of the coupling reaction is colorless.

As the yellow color-forming coupler, various open-chain ketomethylene couplers can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above.

Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention. Ma.

An example of a protective agent is water such as polymethyl methacrylate with a suitable particle size (preferably a particle size of 0.3 to 5 μm or a particle size of at least 2 times, especially 4 times or more, the thickness of the protective layer). Organic compounds such as dispersible vinyl polymers or inorganic compounds such as silver halide, barium strontium sulfate, etc. are preferably used. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties of motion picture films related to camera compatibility during exposure or projection; a specific example is liquid paraffin. , waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, silicones such as polyalkylpolysiloxanes, polyalkylpolysiloxanes, polyalkylarylpolysiloxanes, or their alkylene oxide addition derivatives, etc. is preferably used.

The silver halide photographic material of the present invention may also be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary.

Specifically, silver halide photographic materials using the silver halide photographic emulsion of the present invention include X-ray photographic materials, Lith photographic materials, black and white photographic materials, color negative photographic materials,
Examples include color reversal photosensitive materials and color photographic paper.

Various other additives may be used in the silver halide photographic material of the present invention, if necessary. For example, dyes, development accelerators, optical brighteners, color anticaprilants, ultraviolet absorbers, and the like. Specifically, research disclosure (RESEARCHDISCLO3URE)
No. 176, pages 28-30 ([?D-17643.19
The method described in 1978) can be used.

Furthermore, in the present invention, a compound that releases iodide ions (for example, potassium iodide) can be contained in the silver halide emulsion, and a desired image can be obtained using a developer containing iodide ions.

In the silver halide photographic material of the present invention, the emulsion layer and other layers are coated on one or both sides of a flexible support commonly used in photographic materials.

Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. - (for example, polyethylene, polypropylene, ethylene/butene copolymer), etc. coated or laminated paper. The support may be colored using dyes or pigments. It may be black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoat treatment is performed according to Japanese Patent Application Laid-open No. 52-104913, No. 5
The treatments described in Japanese Patent No. 9-18949, Japanese Patent No. 59-19940, and Japanese Patent No. 59-19941 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The present invention can be used for any photographic material that requires high sensitivity or high contrast. For example, X-ray photographic materials, lithographic photographic materials, black and white negative photographic materials, Used in color negative photosensitive materials, color paper photosensitive materials, etc.

It can also be used in diffusion transfer light-sensitive materials, color diffusion transfer light-sensitive materials, etc., in which a positive image is produced by dissolving undeveloped silver halide and precipitating it on an image-receiving layer close to a silver halide emulsion layer.

For photographic processing of the silver halide photographic light-sensitive material of the present invention, for example, Research Disclosure (Re-search Disclosure)
h Disclosure) No. 176, pages 28-30 (
Any of the various methods and various treatment liquids as described in RD-17643) can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. The processing temperature is usually chosen between 18°C and 50°C, but
The temperature may be lower than 50°C or higher than 50°C.

For example, developers used in black-and-white photographic processing can include known developing agents.

As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-〇-aminophenol), etc. are used alone or in combination. be able to. For photographic processing of the silver halide photographic light-sensitive material of the present invention, Japanese Patent Application No. 55-155
It is also possible to process with a developer containing imidazoles as a silver halide solvent as described in No. 489. It is also possible to process with a developer containing a silver halide solvent and an additive such as indazole or triazole as described in Japanese Patent Application No. 136267/1982. The developer generally contains other known preservatives, alkaline agents, pH buffers, anti-capri agents, etc., and if necessary, a solubilizer, a color toning agent,
It may also contain a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like.

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" development processing is a process in which dihydroxybenzenes are usually used as a developing agent and the development process is carried out at a low sulfite ion temperature for the photographic reproduction of line images or the halftone dot photographic reproduction of halftone images. Refers to a developing process that is carried out contagiously. Among photosensitive materials,
For example, a method may be used in which the photosensitive material is included in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution to perform development. Among the developing agents, hydrophobic ones are described in Research Disclosure No. 169 (RD-16928), U.S. Patent No. 2.739.
, 890, British Patent No. 813.253 or West German Patent No. 1,547,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

When performing color photographic development processing, for example, a negative-positive method, a color reversal method, a silver dye bleaching method, etc. are used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N- Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-methanesulfamide ethylaniline, 4-amino-
3-Methyl-N-ethyl-N-β-methoxyethylaniline, etc.), F. A. Mason, Photographic Process Chemistry, Focal Press.
ssing Chem 1stry, Focal P
ress), 1966, pp. 226-229, U.S. Pat.

The color developer may also contain a pH buffer, a development inhibitor, an antifoggant, and the like. In addition, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, and antioxidants are added. It may also include.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. On the bleaching side, p e + 3, Go”
Compounds of polyvalent metals such as , Cr", Cu", peracids, quinones, nitroso compounds, etc. are used.

For bleach or bleach-fix solutions, see U.S. Patent No. 3,042,52.
No. 0, No. 3,241,966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thioether compound described in JP-A-53-65732, various additives can also be added.

Exposure for the photographic emulsion used in the present invention varies depending on the state of optical sensitization, purpose of use, etc., but includes tungsten, fluorescent lamps, mercury lamps, arc lamps, xenon, sunlight, xenon flash, cathode ray tube flying spot, laser light,
Various types of light sources such as electron beams, X-rays, and fluorescent screens for X-ray photography can be used as appropriate.

In addition to normal exposure of 1/1000 to 100 seconds, the exposure time is 1/1000 to 100 seconds for xenon flash, cathode ray tube, and laser light.
A short exposure of /10' to 1/109 seconds can be applied.

[Embodiments of the invention]

The present invention will be further explained below with reference to Examples.

It goes without saying that the present invention is not limited to the examples.

Example 1 (1) Preparation of polydisperse emulsion A polydisperse emulsion [A] was prepared by a forward mixing method.

i.e. First, four types of solutions are prepared.

Solution B and solution C were poured into a reaction vessel for emulsion preparation and stirred with a propeller type stirrer at a rotation speed of 300 revolutions/minute, and the reaction temperature was maintained at 55°C. Next, the solution A was divided into 1 volume: 2 volumes, and 1 volume, 100 ml, was added over 1 minute. After continuing stirring for 10 minutes, the remaining 2 volumes of Solution A, 200 ml, were added over 2 minutes, and stirring was continued for an additional 30 minutes. Then, Solution D was added to adjust the pH of the solution in the reaction vessel to 6, and the reaction was stopped. In this way, a polydispersed emulsion (A) was obtained. This emulsion contains silver iodide 2.
The average particle size of the particles was 1.21 μm.

Next, the above emulsion was desalted by a conventional agglomeration method, and then 60 mg of ammonium thiocyanate was added to the desalted emulsion.
1 mol of silver halide, 1 mg of chloroauric acid/1 mol of silver halide, 2 mg of sodium thiosulfate/1 mg of silver halide
Mol, 4-hydroxy-6-methyl-1,3,3a,7
-Titrazaindene (stabilizer) Ig/halogenated 111
Gold to sulfur sensitization was carried out by adding 1 mol of gold to sulfur to obtain a photosensitive silver iodobromide emulsion (a).

(2) Preparation of Emulsion (b) Having Internal Fog A silver nitrate aqueous solution and a potassium bromide aqueous solution were simultaneously added to a 2.5% by weight aqueous gelatin solution kept at 55°C. After the addition, the temperature of the solution was maintained at 70° C., potassium hydroxide and silver nitrate were added, and the solution was aged for 20 minutes to form fog nuclei. Thereafter, the solution is kept at 55°C and neutralized by adding acetic acid, then a silver nitrate aqueous solution and a potassium bromide aqueous solution are added simultaneously to form a coating, desalted by a normal flocculation method, and redispersed in an aqueous gelatin solution. The average particle size was 0.40. An emulsion with crm internal fog was obtained. 120 mg of 5-mercapto-1-phenyltetrazole per mole of silver halide was added to this emulsion to obtain emulsion B having internal fog.

(3) Preparation of test sample The photosensitive silver halide emulsion fa) prepared in (1) above and the emulsion (bl) having internal fog prepared in (2) were mixed in a weight ratio of 2:1, To this, polyhydric alcohol according to the present invention was added as shown in Table 1, and nitrone was added at 200 mg/silver halide 1 mol.
2.4-monodihydroxybenzenesulfonic acid sorta t-
1.5 g/1 mole of silver halide and a copolymer of styrene and maleic acid were added to Ig/1 mole of silver halide, and then coated on both sides of a polyester film base that had been primed by the method described in JP-A-59-19941. did.

Furthermore, a protective layer was formed by applying an aqueous gelatin solution having the following composition onto each emulsion surface.

The amount of silver coated on both sides was 4.5 g/m, the amount of gelatin coated on the protective layer was 2.6 g/rrr on both sides, and the amount of gelatin coated on the emulsion layer was 4.0 g/m.

Composition of gelatin aqueous solution (4) Test method of test sample The sample prepared above was wedge-exposed at 3.2 CMS, and was processed using XD-90 processing solution and XF using a QX-1200 automatic processor manufactured by Konishiroku Photo Industry Co. Developing temperature: 31"C with fixing processing solution, 90°C at 135°C and 37°C, respectively.
After second development, photographic performance was measured and the results shown in Table 1 were obtained.

As comparative samples, those coated with only a photosensitive silver halide emulsion and those coated with only an emulsion having internal fog with similar silver ffl and gelatin amounts were used.

In addition, the following compounds were used as polyhydric alcohol comparison compounds.

” This L Yuusai (a) Ethylene glycol -12.6℃ (
b) 1,4-butanediol 16℃ (c) Glycerin 18.2℃ (d) 1,2,6-hexandriol -20℃ 1st
The sensitivity in the table is the reciprocal of the exposure amount required to obtain a transmitted light blackening density of "fog value + 1.0", and is expressed as a relative value with the development temperature of sample 1 at 35° C. as 100. Also, gamma is "Capri value + 0.2" and "Fog + 1.0"
The slope value of the characteristic curve between Note that the Capri value is a value that includes the base density. Furthermore, the compound (A) used in Example 2 of JP-A-60-166944 was used as a comparative compound.

As is clear from Table 1, samples Nos. 10 to 18 using the compounds of the present invention showed the following: Hit, 7° Compound (A)
The gamma variation range is small and the processing temperature dependence is good.

This means that compared to conventional silver halide photographic materials in which polyhydric alcohols functioned as sensitizers, in so-called "trigger-sensitive materials" they have a completely different function. .

That is, it seems that polyhydric alcohols with low melting points quickly flow out of the film during high-temperature treatment, making it impossible to satisfactorily control the "trigger effect." Example 2 (11 Preparation of photosensitive silver halide emulsion A polydisperse emulsion [C] was prepared in the same manner as in Example 1. This emulsion contained 4 mol% of silver iodide, and the average grain size of the grains was 1.
It was 2 μm. Next, the above emulsion was desalted by a conventional agglomeration method, and then 50 mg of ammonium thiocyanate was added to the emulsion.
1 mole of silver halide, 0.8 mg of chloroauric acid/1 mole of silver halide, and 1.6 mg/1 mole of sodium thiosulfate were added to perform gold-sulfur enrichment, and as a stabilizer, 4-hydroxy- The same amount of 6-methyl-1,3,3a,7-chitrazaindene as in Example 1 was added to obtain a photosensitive silver iodobromide emulsion (C).

(2) Preparation of emulsion with internal fog Cu containing 3°0 mol% Cul with an average grain size of 0.2 μm was prepared by the method of Example 2 of JP-A-58-116535.
Br 1 particles were prepared, and without water washing and desalting treatment, Capri nuclei were subsequently formed by light. After that, a coating was formed by the same operation using an appropriate amount of the same solution,
The emulsion was washed with water and desalted as described in Example 1 of JP-A-58-116535, and then redispersed in an aqueous gelatin solution to obtain an emulsion with an internal fog having an average particle size of 0.40 μm.

(3) Preparation of test sample It was produced in the same manner as in Example-1.

(4) Test method for test samples The photographic performance was measured in the same manner as in Example-1, and the results shown in Table 2 were obtained.

After being treated in the same manner as in Example-1, as is clear from Table 2, samples Nl1IO-18 using the compound of the present invention were
Changes in fog, sensitivity, and gamma due to processing temperature changes are small, and processing temperature dependence is good.

Margins below - [Effects of the Invention] As described above, according to the present invention, a silver halide photographic material that provides images with high sensitivity, high contrast, and high maximum density can be obtained.

Further, according to the present invention, a silver halide photographic material can be obtained which can suppress the generation of capri and extremely increased sensitivity and changes in gradation, especially during high temperature rapid processing.

In other words, according to the present invention, a silver halide photographic material that always provides stable photographic performance can be obtained.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Toru Takatsuki Procedural Amendment (Voluntary) 1939! June 9th, Commissioner of the Patent Office, Kuro 1) Mr. Akihiro 1, Indication of the case, 1988 Patent Application No. 011427 2, Name of the invention, Silver halide photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant's address Tokyo 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Konishiroku Photo Industry Co., Ltd. 4, Agent

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, the photographic light-sensitive material comprising: light-sensitive silver halide grains on the support; A silver halide photographic material comprising metal salt particles having fog and a polyhydric alcohol having a melting point of 40° C. or higher and having at least two hydroxyl groups.