JPH0766158B2 - Negative-type silver halide photographic light-sensitive material with high sensitivity and improved sea flight fog - Google Patents

Description

TECHNICAL FIELD The present invention relates to a negative type silver halide photographic light-sensitive material with improved safelight fog, which has particularly high sensitivity, excellent pressure resistance, and resistance to scratches between films. Is good,
The present invention also relates to a negative-type silver halide photographic light-sensitive material having good safelight resistance.

[Prior art]

In recent years, applications of photographic light-sensitive materials have been expanding, and for this reason, silver halide photographic light-sensitive materials having higher sensitivity and improved pressure resistance have been actively developed, and various technologies have been disclosed. There is.

However, with the increase in sensitivity of photographic light-sensitive materials, new problems such as deterioration of safelight resistance have begun to appear.

Particularly in recent years, the spread of ortho films has been remarkable, and the problem of safe light fog against relatively bright ortho safe lights has become a problem.

To improve the sensitivity, pressure resistance and safelight resistance of the silver halide photographic light-sensitive material, it is described in JP-A-59-99433, 59-178447 and 60-35726. Such an internal high iodine-containing type silver halide grain may be used. Then, the photographic light-sensitive material using the silver halide grains having a high content of internal iodine is resistant to safe light glass for orthofilm (for example, highlight: manufactured by Konishi Roku Photo Industry Co., Ltd., GBX: manufactured by Eastman Kodak Co., Ltd.). The photographic performance and characteristics including the safelight property are also relatively good. However, the photographic performance and characteristics including the above-mentioned safelight resistance are problematic in that they tend to deteriorate rapidly when the silver halide grains have a large grain size or when the degree of chemical ripening becomes excessive. It was

[Object of the Invention]

An object of the present invention is to provide a negative-type silver halide photographic light-sensitive material having high sensitivity, excellent pressure resistance, good scratch resistance between films, and good safelight resistance.

[Structure of Invention]

The above-mentioned object is a photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer in the emulsion layer contains chemically sensitized silver halide grains, and Has an average iodine content of 4 mol% or less as the whole halogen composition, and
An internal high iodine-containing type having a portion having a high average iodine content of 10 mol% or more, and further containing 1.6 × 10 ⁻³ mol or more of thiocyanate per 1 mol of total silver on the side having the emulsion layer, And all binders on the side having the emulsion layer
It is achieved by a negative type silver halide photographic light-sensitive material containing 0.04 to 0.25 g of a polyhydric alcohol which is a compound having a molecular weight of 150 or less per 1 g and in which two or more hydrogen atoms of an aliphatic hydrocarbon are substituted with a hydroxyl group.

If the sensitivity is increased under the conditions other than the above, the safelight sensitivity increases and the safelight resistance deteriorates.

In order to sufficiently bring out the effects of the present invention, it is preferable that the proportion of the internal high iodine-containing grains in all the silver halide grains is large.

The photographic light-sensitive material having at least one silver halide emulsion layer on the support in the present invention means that at least one silver halide emulsion layer is provided on at least one surface of the support.
It means a state in which layers are formed. Further, a non-photosensitive layer may be formed on at least one surface of the support. When two or more silver halide emulsion layers are formed on at least one surface of the support, at least a non-photosensitive layer is provided between these silver halide emulsion layers. The above-mentioned non-photosensitive layer means an underlayer, an intermediate layer, a protective layer, an antihalation layer, a filter layer and the like.

The support is not particularly limited as long as it is generally used as a substrate of a silver halide photographic light-sensitive material.

Further, the average iodine content referred to in the present invention refers to JP-A-60-
Electron Probe Micro A described in Japanese Patent 143331
It is obtained by the nalyzer (electron probe microanalyzer) method and the X-ray diffraction method.

Further, the particle surface in the present invention means that the depth from the particle surface is
It means a portion of 0.05 μm or less, and the inside of the particle means a portion where the depth from the particle surface exceeds 0.05 μm. Further, the average iodine content of the particle surface in the present invention is an average iodine content percentage as a halogen of a portion having a depth of 0.05 μm or less from the particle surface, and the average iodine content inside the particle is from the particle surface. It is the average percentage of iodine contained as halogen in the portion where the depth exceeds 0.05 μm.

In the internal high iodine-containing particles, if the average iodine content of the particles as a whole exceeds 4 mol%, the effect of the present invention is not readily obtained. Further, when there is no high iodine-containing portion inside the particle (portion higher than the surface by 10 mol% or more) or when the average iodine content on the particle surface is large (3 mol% or more), the effect as in the present invention is obtained. Is not obtained, but it is small if obtained.

The photographic light-sensitive material of the present invention may be spectrally sensitized.
For example, it is preferable to carry out spectral sensitization by the method described in Research Disclosure Vol. 176, pages 22 to 28 (December 1978), and especially Japanese Patent Publication Nos. 43-22884 and 48-28293. JP, 48-41203, JP 49-
It is preferable to use the methods described in No. 12656, No. 48-41205, No. 48-56425, No. 47-25379, No. 45-18443.

The internal high iodine-containing silver halide grains used in the present invention are
JP-A-59-99433, JP-A-59-178447, JP-A-60-3
As described in Japanese Patent No. 5726 and the like, it is preferable that the silver solution and the halogen solution are simultaneously mixed at least during one stage of grain formation while controlling pAg and pH.

The silver halide grains contained in the photographic light-sensitive material of the present invention may be partially provided with a high iodine-containing portion on the surface after the grain growth by an iodine substitution method or the like. However, the high iodine-containing portion has a high iodine content within the scope of the present invention described above in the relationship between the average iodine content of the inside and the surface of the silver halide grain and the average iodine content of the entire silver halide grain. It goes without saying that it is done.

The total amount of the binder on the side containing the internal high-iodine silver halide grains used in the present invention is preferably in the range of 50 to 800 g, particularly 80% on the basis of 1 mol of the total silver halide on the side containing the silver halide grains. A range of up to 400 g is preferred.

The internal high iodine-containing particles used in the present invention preferably have a particle diameter of 10 times or less the particle thickness, and if the particle diameter is 10 times or less, a cube, an octahedron, or an intermediate shape or a rounded surface. Or it may be a flat plate.

The amount of thiocyanate used in the present invention is 1.6 × 10 ^−3.
If it is more than the molar amount, the sensitivity is increased and the safe light resistance is remarkably improved. If the amount of thiocyanate added is less than 1.6 × 10 ⁻³ mol, the sensitivity cannot be increased and the safelight resistance cannot be improved.

If too much thiocyanate is added, it is easy to cause a scratch failure between films when the commercialized light-sensitive material is left in a high-humidity atmosphere, so 1 mol of silver [g] / total hydrophilic binder [g] = In the range of 0.5 to 2.0 per mol of silver
Especially preferred is between 130 and 1000 mg.

Further, the addition amount of the polyhydric alcohol having a molecular weight of 150 or less is less than 0.04 g per 1 g of the total binder on the side having the emulsion layer of the present invention, the safelight property, the effect of improving pressure resistance is hardly seen, and the amount is more than 0.25 g. Kutski between the films at high temperature is likely to occur.

The thiocyanate used in the present invention is an alkali metal thiocyanate, an alkaline earth metal thiocyanate, ammonium thiocyanate, etc. Among them, an ammonium thiocyanate or an alkali metal thiocyanate is preferable. These thiocyanates may be used alone or in combination of two or more.

The polyhydric alcohol used in the present invention is a compound in which two or more hydrogen atoms of an aliphatic hydrocarbon are replaced with hydroxyl groups,
It has a molecular weight of 150 or less. If the molecular weight is larger than this, it is difficult to obtain the effect of improving the safelight property and the pressure resistance is not so effective.

Specific examples of the polyhydric alcohol having a molecular weight of 150 or less are shown below, but the present invention is not limited to these specific examples.

(Compound name) (Molecular weight) 1. Diethylene glycol 62 2.2,3-Dihydroxybutane 90 3. Glycerin 92 4.2,2-Dimethyl-1,3-propanediol 104 5.2-Butyne-1,4-diol 86 6.2,5-hexane Diol 118 7.1,6-Hexanediol 118 8.2,4-Hexadiyne-1,6-diol 110 9.2,3,4-Hexanetriol 134 10.2-Methyl-2-oxymethyl-1,3-propanediol 120 11.Erythritol 122 12.D-Trait 122 13.L-Trait 122 14.2,2-Dihydroxymethyl-1-butanol 134 15.Pentaerythritol 136 16.2,3,4,5-Hexanetetrol 136 17.1,2,3,4-Pen Tantetrol 136 18.3-hexyne-1,2,5,6-tetrol 146 19.2,6-octadiyne-1,8-diol 138 20.2-methyl-2,3,4-butanetriol 119 21,2,4-dimethyl- 2,3,4-Pentanetriol 148 22.2,2-Dimethy -1,3-Pentanediol 104 23.1,8-Octanediol 146 24.3-Hexene-1,2,5,6-tetrol 148 The above-exemplified compounds may be used alone or in combination of two or more. Good. When two or more types are mixed and used,
If at least one kind has a molecular weight of 150 or less, the other may have a molecular weight larger than 150. However, even in the case of a mixture, the content of polyhydric alcohol with a molecular weight of 150 or less is
It goes without saying that the range is 0.04 to 0.25 g per g.

Gelatin (hydrophilic) is advantageously used as the binder or protective colloid of the emulsion in the photographic light-sensitive material of the present invention, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used alone or in combination of two or more.

Gelatin includes lime-processed gelatin, acid-processed gelatin, and Bulletin of Society of Science of Photography of Japan (Bull.So.
c.Sci.Phot.Japan) No. 16, page 30 (1966), an enzyme-treated gelatin may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.

If desired, various materials such as stabilizers and thickeners can be added to the photographic light-sensitive material of the present invention.

The photographic emulsion used in the present invention is described by P. Glafkides, Chemie et Physik Photography (Chimie et.
Physique Photographique, published by Paul Montel, 1976
Year), by GHDuffin, Photographic Emulsion Chemistr
y), The Focal Press, 1966), VLZelikman et
Making and Coating Photograp by al.
hic Emulsion, The Focal Press, 1964) and the like. That is,
Any of the acidic method, the neutral method, the ammonium method, etc.,
As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
To keep constant, that is, so-called control
The double jet method can also be used.

According to this control double jet method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

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

During the silver halide formation, physical ripening, chemical ripening or coating process, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, etc. are allowed to coexist. Good.

The emulsion used in the present invention usually removes soluble salts after the formation of a precipitate or after physical ripening. As a means therefor, the Nudel washing method in which gelatin is gelatinized may be used, and the emulsion is composed of a polyvalent anion. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid), or gelatin derivatives (such as aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin)
You may use the sedimentation method (flocculation) which utilized. The process of removing soluble salts may be omitted.

The light-sensitive silver halide emulsion may be used as it is, as it is, as a so-called unripened (Primitive) emulsion without chemical sensitization, but it is usually chemically sensitized. For chemical sensitization,
Glafkides or Zelikman et al., Or H. Fri
eser ed. de Grundlagen del photography Shen Protzese Mito Gilberhalogeneden (Di
e Grundlagen der Photographischen Prozessemit Silb
erhalogeniden, Akademische Verlagsgesellschaft, 19
The method described in 68) can be used.

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitizing method using a reducing substance, a noble metal sensitizing method using gold or other noble metal compounds, etc., alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
2,410,689, 2,278,947, 2,728,668, and 3,656,955. Examples of the reduction sensitizers include primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds. Specific examples thereof are U.S. Pat.
2,419,974, 2,518,698, 2,983,609, 2,983,610, and 2,694,637. For sensitizing precious metals, in addition to gold complex salts, platinum, iridium,
A complex salt of a metal of Group VII of the periodic table such as palladium can be used, and specific examples thereof are disclosed in US Pat. No. 2,399,083 and US Pat.
2,448,060, British Patent No. 618,061 and the like.

Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of 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 (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-
5-mercaptotetrazole), mercaptopyridines, the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group, thioketo compounds such as oxazoline thione, azaindenes such as tetraazaindenes (especially 4-hydroxy substitution ( 1,3,3a, 7)
Tetraazaindenes), benzenethiosulfonic acids,
Many compounds known as stabilizers can be added such as benzenesulfinic acid and the like.

An example of a compound that can be used is K. Mees, The Theory
The Theory o
f the Photographic Process, 3rd edition, 1966).

For more detailed specific examples of these and methods for using them, reference can be made to, for example, U.S. Pat. Nos. 3,954,474, 3,982,947, 4,021,248 and Japanese Patent Publication No. 52-28660.

In the production method of the present invention, the pH of the coating liquid is preferably in the range of 5.8 to 7.5. In the case of multi-layer coating, the pH of the coating liquid prepared by mixing the coating liquids of the respective layers in the coating amount ratio is preferably in the above range of 5.8 to 7.5. If the pH is lower than 5.8, the dura mater progresses slowly, which is not preferable, and the pH is 7.
If it is larger than 5, the photographic performance is often adversely affected, which is not preferable.

The photographic emulsion layer or other constituent layers of the silver halide photographic light-sensitive material according to the present invention include a coating aid, an antistatic agent, a slip property improving agent, an emulsion dispersion agent, an adhesion preventing agent and a photographic characteristic improving agent (for example, development acceleration, contrast enhancement, A surfactant other than the present invention may be included for various purposes such as sensitization).

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Alkyl amides or amides, polyethylene oxide adducts of silicone), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars, alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl- N-alkyl taurate sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates such as carboxy groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups, etc. Anionic surfactants containing acidic groups, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, amphoteric surfactants such as alkylbetaine acid, amine oxides, alkylamine salts, aliphatic or aromatic compounds Class a Moniumu salts, pyridinium, can be used a heterocyclic quaternary ammonium salts such as imidazolium, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic ring.

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

In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

Further, the silver halide photographic light-sensitive material of the present invention can contain the alkyl acrylate latex described in U.S. Pat. Nos. 3,411,911, 3,411,912 and JP-B-45-5331 in the photographic constituent layers.

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

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by 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 normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei, such as tetrazole nucleus and pyridine nucleus, and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus , Benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei are
It may be substituted on the carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

The sensitizing dye used in the present invention is used in the same concentration as that used in a normal negative type silver halide emulsion. In particular, it is advantageous to use a dye concentration that does not substantially reduce the intrinsic sensitivity of the silver halide emulsion. About 1.0 × 10 ⁻⁵ to about 5 × 10 ⁻⁴ mol of the sensitizing dye is preferable per mol of silver halide, and about 4 × of the sensitizing dye per mol of silver halide is particularly preferable.
It is preferably used at a concentration of 10 ^{−5 to} 2 × 10 ⁻⁴ molar.

The silver halide emulsion used in the present invention contains a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) which reacts with an oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. May be included. The coupler is preferably a non-diffusible type having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Also, a colored coupler having a color correction effect, or a coupler that releases a development inhibitor upon development (so-called DIR coupler).
May be included. The coupler may be such that the product of the coupling reaction is colorless.

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

As the magenta coupler, a pyrazolone compound, an indazolone compound, a cyanoacetyl compound or the like can be used, and the pyrazolone compound is particularly advantageous.

As the cyan coupler, a phenol compound, a naphthol compound or the like can be used.

The protective layer of the silver halide photographic light-sensitive material according to the present invention is a layer composed of a hydrophilic colloid, and the hydrophilic colloid used is the one described above. Further, the protective layer may be a single layer or multiple layers.

A matting agent and / or a leveling agent may be added to the emulsion layer or protective layer of the silver halide photographic light-sensitive material of the present invention, preferably in the protective layer. Examples of the matting agent include polymethylmethacrylate having an appropriate particle size (particle size of 0.3 to 5 μm, or preferably 2 times or more, more preferably 4 times or more the thickness of the protective layer). An organic compound such as a water-dispersible vinyl polymer or an inorganic compound such as silver halide or strontium barium sulfate is preferably used. Similar to the matting agent, the leveling agent is useful for preventing adhesion failure, and is particularly effective for improving the frictional characteristics related to the camera suitability during shooting or projection of motion picture film. Specific examples include liquid paraffin. Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or silicones such as their alkylene oxide addition derivatives. Is preferably used.

The silver halide photographic light-sensitive material of the present invention may be optionally provided with an antihalation layer, an intermediate layer, a filter layer and the like.

Various additives can be used in the silver halide photographic light-sensitive material of the present invention, if necessary. Examples thereof include dyes, development accelerators, optical brighteners, antifoggants, and ultraviolet absorbers. Specifically, Research Disclosure No. 176, pp. 28-30 (RD
-17643, 1978) can be used.

Further, in the present invention, a compound capable of releasing iodide ions (eg potassium iodide) can be contained in the silver halide emulsion, and a desired image can be obtained by using a developing solution containing iodide ions.

In the practice of the silver halide photographic light-sensitive material of the present invention, for example, an emulsion layer and other layers can be formed by coating one side or both sides of a flexible support usually used for photographic light-sensitive materials. What is useful as the flexible support is a film, a baryter layer or an α-olefin polymer made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, or polycarbonate. Examples include paper coated or laminated with (for example, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. It may be black for the purpose of light shielding. The surface of these supports is generally subbed to improve adhesion with emulsion layers and the like. The undercoat treatment is disclosed in JP-A-52-104913.
59-18949, 59-19940, 59-19941
The treatment described in the publication is preferred.

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

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

The silver halide photographic light-sensitive material of the present invention can be applied to any kind. Specifically, an X-ray photosensitive material, a lith photosensitive material, a black and white photographic photosensitive material, a color negative photosensitive material, a color reversal photosensitive material, a color printing paper, or the like, or a diffusion transfer negative photosensitive material having an internal fog nucleus, a diffusion transfer having an internal fog nucleus. A positive photosensitive material can be mentioned.

Further, it can also be used for a diffusion transfer photosensitive material, a color diffusion transfer photosensitive material, etc., which forms a positive image by dissolving undeveloped silver halide and precipitating it on the image receiving layer adjacent to the silver halide emulsion layer.

The photographic processing of the silver halide photographic light-sensitive material according to the present invention is
Various methods can be used without particular limitation. For example, any of various methods and various processing solutions such as those described in Research Disclosure No. 176, pages 28 to 30 (RD-17643) can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually selected between 18 ° C and 50 ° C,
The temperature may be lower than 18 ° C or higher than 50 ° C.

For example, the developer used for black and white photographic processing may contain a developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone),
Aminophenols (for example, N-methyl-o-aminophenol) and the like can be used alone or in combination. For the photographic processing of the silver halide photographic light-sensitive material of the present invention, it is also possible to perform processing with a developing solution containing an imidazole as a silver halide solvent described in Japanese Patent Application No. 55-155489. Further, it can be processed with a developing solution containing a silver halide solvent described in Japanese Patent Application No. 56-136267 and an additive such as imidazole or triazole. The developer generally contains various other preservatives, alkali agents, pH buffers, antifoggants, and the like, and further contains a solubilizing agent, a color toning agent, a development accelerator, a surfactant, an antifoaming agent, if necessary. , A curing / softening agent, a hardener, a viscosity-imparting agent and the like may be contained.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. The "lith-type" development process is a development process in which dihydroxybenzenes are usually used as a developing agent and a low sulfite ion temperature is used for the photographic reproduction of a line image or the halftone image by a halftone image. Is a contagious development process (details are described in Mason's "Photographic Processing Chemistry" (1966), pages 163-165.) As a special form of development process, a developing agent In the photosensitive material,
For example, a method may be used in which the photosensitive material is contained in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution for development. Hydrophobic developing agents are research disclosure
169 (RD-16928) U.S. Pat. No. 2,739,890, British Patent No. 813,253, West German Patent No. 1,547,763 and the like can be incorporated into the emulsion layer by various methods. Such a development treatment may be combined with a silver salt stabilization treatment with thiocyanate.

As the fixer, a fixer having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixer 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 or the like is used.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are primary aromatic amine developers such as phenylenediamines (eg 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-
Methanesulfonamide ethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline, etc. and LFA Mason: Photographic Proceeding Chemistry, published by Focal Press (Phot.
ographic Processing Chemistry, Focal Press), 1966
Year, pages 226-229, U.S. Pat.Nos. 2,193,015 and 2,592,3
No. 64, JP-A-48-64933, etc. may be used.

The color developing solution may further contain a pH buffer, a development inhibitor or an antifoggant. If necessary, a water softener, a preservative, an organic solvent, a development accelerator, a dye-forming coupler, a competitive coupler, a fogging agent, an auxiliary developing solution, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant. Etc. may be included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed separately. Bleaching agents include Fe ⁺³ , Co ⁺⁴ , Cr ⁺⁶ , Cr
Compounds of polyvalent metals such as ⁺² , peracids, quinones, nitroso compounds and the like are used.

For bleaching or bleach-fixing solutions, U.S. Pat.No. 3,042,520,
No. 3,241,966, JP-B-45-8506, JP-B-45-8836
In addition to the bleaching accelerators described in JP-A No. 53-65732, various additives may be added.

The exposure to the photographic emulsion used in the present invention varies depending on the state of chemical sensitization, purpose of use, etc., but is different from tungsten, fluorescent lamp, mercury lamp, arc lamp, xenon sunlight, xenon flash, cathode ray tube flying spot, laser beam, electron beam. Various light sources such as X-rays, X-rays, and fluorescent screens during X-ray imaging can be used as appropriate.

The exposure time is from 1/100 to 100 seconds for normal exposure, and 1/10 ⁴ to 1/1 for xenon flash, cathode ray tube, and laser light.
A short exposure of ⁰⁹ seconds can be applied.

〔Example〕

Hereinafter, the present invention will be further described with reference to examples. Needless to say, the present invention is not limited to the examples.

Example 1 Preparation of Sample A comparative polydisperse emulsion was prepared by the forward mixing method.

That is, the above-mentioned four kinds of solutions (solutions A to D) were first prepared.

Then, the solutions B and C were poured into a reaction kettle for emulsion preparation and stirred with a propeller-type stirrer at a rotation speed of 300 rpm to keep the reaction temperature at 55 ° C. Subsequently, the solution A was divided into a volume of 1: 2 and 1 volume of 100 ml was added to the mixed solution of the solution B and the solution C over 2 minutes. After continuing stirring for 10 minutes, 200 ml of the remaining 2 volumes of solution A was further added over 3 minutes, and stirring was continued for 30 minutes. Then, D solution was added to the mixed solution of A solution, B solution and C solution to adjust the pH of the solution in the reaction vessel to 6 to stop the reaction. Thus, a comparative polydisperse emulsion having an average grain size of 1.21 μm (Table 1, sample No .: comparison) was obtained.

Then, a silver chloroiodobromide emulsion containing 2.0 mol% of silver iodide and 1.0 mol% of silver chloride and having an average grain size of 0.3 μm was prepared at 60 ° C., pAg = 8, pH = 2.
It was manufactured by the double jet method while adjusting to 0. When an electron micrograph of this emulsion was taken, it was found to be a monodispersed cubic crystal emulsion (A) of silver iodobromide having a twin crystal grain generation rate of 1% or less. Seed this emulsion (A) at 40 ℃
A solution 8.5 containing the protected gelatin held in and the ammonia added as necessary was added and dispersed, and a solution whose pH was adjusted by glacial acetic acid was obtained.

Using this solution as a mother liquor, an aqueous 3.2N ammoniacal silver ion solution was added to this mother liquor while controlling the flow rate by the double jet method, and layers with various silver iodide contents were added as shown in Table 1 with halogen ratios and Emulsions No. 1 to No. 1 in Table 1 were obtained by sequentially forming pAg patterns as shown in FIG. That is, the first coating layer was prepared by controlling the pAg at 7.3 and the pH at 9.7 at a ratio of potassium iodide 8 to 30 mol% and potassium bromide 92 to 70 mol%, and the outermost layer was potassium iodide 0 to 0.2. Mol%, potassium bromide 100-99.8 mol% pAg 9.0
Was controlled to be prepared. The timing of switching the halogen ratio and pAg, that is, the timing of shifting from the formation of the first coating layer to the formation of the outermost layer is as shown in FIG. Emulsion Nos. ~ Were prepared as described above.

The emulsions thus prepared all have an average grain size of 1.20 μm.
It was a monodisperse emulsion of m. The iodine content of the grains was determined by the Electron Probe Micro Anylyzer method described above, and the average silver iodide content at a depth of 0.05 μm or less from the surface of the grain and 0.05 from the surface of the grain. The value of the point having the highest silver iodide content at a depth of more than μm was measured. The measured values are shown in Table 1.

Then add a second emulsion to each emulsion per mole of silver halide.
The amounts of ammonium thiocyanate shown in the table, 1 × 10 ^-6 mol of chloroauric acid and 2.5 × 10 ^-5 mol of hypo were added to chemically sensitize the silver halide grains. Next, an emulsion coating solution was prepared by adding 12.6 g of the polyhydric alcohol of Exemplified Compound No. 14 per mol of silver halide, 84 g of lime-processed gelatin, a usual stabilizer and a usual thickener.

A liquid having the following composition was prepared as a protective liquid.

The 19 types of emulsion solutions obtained as described above and the above-mentioned protective layer solution were simultaneously coated at a speed of 150 m / min on a transparent polyethylene terephthalate film having a thickness of 175 μm by a slide hopper coater under the following conditions. , Set the cooling, dry the initial dry-bulb temperature 28 ℃, zero -3.0 ℃, middle-stage dry-bulb temperature 30 ℃, dew point 9 ℃, late-stage dry-bulb temperature 33 ℃, send dew point 25 ℃ 2 minutes After drying for 30 seconds, sample No. 1 to 23 in Table 2
Got

(Coating conditions) Relative sensitivity measurement method Wedge exposure was performed on each sample with 3.2 CMS, and XD-90 was used with Konishi Rokusha Kogyo Co., Ltd. (KX-500) automatic processor.
After processing for 90 seconds with a developing solution, the sensitivity of each sample was determined.

The sensitivity was calculated by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0 by exposure, and expressing it as a relative value with the sensitivity of No. 1 in Table 2 being 100.

Pressure resistance test method Two pieces of each of the obtained samples were kept at a constant temperature and humidity of 25 ° C and a relative humidity of 35% for about 12 hours.
It was bent about 280 ° at m.

One of the two sheets was developed 3 minutes after folding and was left unexposed. The difference between the density of the blackened portion and the fog density caused by the bending at this time was set as ΔD _{1 and used} as a standard for pressure blackening. That is, the smaller this value, the better the pressure blackening resistance.

The other one of the two sheets was exposed and developed using an optical wedge 3 minutes after bending. Each wedge blackening density of this sample was measured, and the density difference between the desensitized part caused by bending at the density 1.0 ± 0.1 part and the part not bent was ΔD _2, and at each density D ₂ ΔD The average value ΔD ₂ / D ₂ was calculated by dividing by ₂ and this value was used as a guide for pressure desensitization. That is, the smaller this value, the better the pressure desensitization resistance.

Safelight resistance test method Each of the obtained samples was subjected to cherry-blowing under conditions of 25 ° C and 35% relative humidity.
The safelight property was confirmed using a high ortho safelight glass highlight (20 W light bulb, Konishi Rokusha Kogyo Co., Ltd.). The distance from the safelight glass to the sample is 1.
The sample was placed parallel to a safelight glass at 2 m and irradiated for 30 minutes, and the density increase in the fog portion was expressed as ΔD ₃ .

The results of evaluation as described above are shown in Table 2.

As is clear from Table 2, sample No. 6,7,1 according to the present invention
It can be seen that 0, 11, 14, and 15 have high sensitivity and excellent pressure resistance and safelight resistance.

Example 2 Comparative polydisperse emulsions of Table 1 and 1 prepared in Example 1
Using the monodisperse emulsion shown in the table, only the kind and amount of polyhydric alcohol were changed as shown in Table 3, and some of the following comparative compounds a, b and c were used, and the others were sample No. of Table 2. Application was performed in the same manner as in Section 6 to obtain Sample Nos. 24 to 48. Comparative compound molecular weight (a) trans 2,5-dimethyl-3-hexene-2,5-diol 170 (b) 1,12-dodecanediol 202 (c) 1,12-octadecanediol 286 These samples are all Evaluation was performed in the same manner as in Example 1. Moreover, in order to confirm the scratch resistance between the films, the following scratch resistance test was performed.

Heat treatment test for a period of time (Kutsuki resistance test) The same sample that had been conditioned at 25 ° C and 55% RH for 12 hours was overlaid, and a load was applied so that a pressure of 20 g / cm ² was applied, and the film was shielded. The film was placed in a thermostat at 4 ° C. for 4 days for heat treatment, and the Kutsuki degree between the films was evaluated in four grades A to D as follows.

A: No wood cut B: Wood cut area less than 5% C: Wood cut area less than 15% D: Wood cut area 15% or more The measurement results are shown in Table 3. As is clear from Table 3, the samples 25, 26, 29, 30, 34, 35, 36, 38, 39 according to the present invention have all the sensitometric performance, pressure resistance, safelight resistance and knack resistance. It turns out that it is good.

Example 3 Gelatin 32g, potassium bromide 11.0g, and 0.5% of thioether _{(HO (CH 2) 2 S} (CH 2) 2 S (CH 2) 2 OH) aqueous solution 12cc to prepare an aqueous solution in addition to water 1, This aqueous solution at 65 ℃, pA
While maintaining g9.2 and pH 6.6, the total amount of solutions I and II shown in Table 4 was added simultaneously under stirring over 40 seconds, and then the total amount of solution III shown in Table 4 was added over 8 minutes. Then, the total amount of solutions IV and V shown in Table 4 was simultaneously added by the double jet method over 80 minutes to prepare silver halide grains.

The silver halide grains thus obtained have an average diameter of
It was 1.27 μm and the average diameter / thickness ratio was 5.1.

Then, 1 × 10 ^-3 mol of ammonium thiocyanate, 3.5 × 10 ^-5 mol of hypo, 3.5 × 10 ^-6 mol of chloroauric acid, and 5 × 10 ^-5 mol of thiourea were added to 1 mol of silver halide grains, and chemicals were added. Aged and further 1% potassium iodide (KI) aqueous solution 30
cc was added, and further 600 mg of the following sensitizing dyes (A) and 25 mg of (B) were added.

Then, the polyhydric alcohol of Exemplified Compound No. 14 or the comparative compound (a) used in Example 2 and ammonium thiocyanate were added in an amount shown in Table 5 with respect to 1 mol of silver halide. An emulsion coating solution was obtained by adding 120 g of gelatin and usual stabilizers and thickeners. This emulsion coating solution and the protective layer solution used in Example 1 were simultaneously coated on a transparent polyethylene terephthalate film having a thickness of 175 μm by a slide hopper coater under the following conditions at a speed of 150 m / min under the following conditions. Then, the sample was dried under the same drying conditions as in Example 1 (however, only the amount of drying air was changed and dried in 2 minutes and 30 seconds) to obtain sample Nos. 49 to 60 in Table 5.

(Coating conditions) Emulsion liquid: 50 m ² per mol of silver halide Protective layer liquid: 70 m ² per 70 g of gelatin For each sample prepared as described above, the same measurement as in Example 1 was carried out, and the measurement result was the fifth. Shown in the table. However, the relative sensitivity was expressed as relative sensitivity with the sensitivity of Sample No. 45 as 100.

As a result of halogen composition analysis of the grain after dye sensitization, the silver iodide content in the high iodine content portion inside was 27 mol% and the silver iodide content in the surface was 0.7 mol%.

As is clear from Table 5, Sample Nos. 53 and 54 according to the present invention
Indicates that the sensitivity, pressure resistance, and safelight resistance are good.

As can be seen from Examples 1-3, at least one in the emulsion layer
The average iodine content of the whole chemically sensitized silver halide grains in the layer is 4 mol% or less, and there is a portion having 10 mol% or more of the average iodine content higher than the surface inside, and the emulsion layer is 0.04 to 0.25 g of polyhydric alcohol containing 1.6 × 10 ^-3 mol or more of thiocyanate and having a molecular weight of 150 or less per 1 mol of total silver on the side having 1 to 1 g of total hydrophilic binder on the side having the emulsion layer. Only by inclusion (eg Samples 6, 7, 10, 11, 14, 1, 1 of Example 1, Table 2)
5) A negative type silver halide photographic light-sensitive material having high sensitivity, excellent pressure resistance, good scratch resistance between films (hard to scratch), and good safelight resistance can be obtained.

In other words, even if a thiocyanate and a polyhydric alcohol as described above are contained in a silver halide other than the above-mentioned silver halide containing high internal iodine, the excellent effect of the present invention cannot be obtained (for example, Example 1, Sample No. 17 in Table 2
~twenty three). That is, in other than the present invention, if the sensitivity is increased, the safe light resistance is deteriorated.

〔The invention's effect〕

As described above, according to the present invention, a negative type silver halide having high sensitivity, excellent pressure resistance, good scratch resistance between films (hard to scratch), and good safelight resistance. A photographic light-sensitive material is obtained.

[Brief description of drawings]

FIG. 1 is a pAg adjustment pattern when preparing a silver halide emulsion.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-54-159223 (JP, A) JP-A-59-181337 (JP, A) JP-A-59-178447 (JP, A) JP-A-60- 35726 (JP, A) JP 60-147727 (JP, A) JP 61-14636 (JP, A) JP 62-18538 (JP, A) JP 62-89953 (JP, A)

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer in said emulsion layer contains chemically sensitized silver halide grains, and The particles have an average iodine content of 4 mol% or less in terms of halogen composition,
An internal high iodine-containing type having a portion having a high average iodine content of 10 mol% or more, and further containing 1.6 × 10 ⁻³ mol or more of thiocyanate per 1 mol of total silver on the side having the emulsion layer, And all binders on the side having the emulsion layer
Negative-type silver halide photographic light-sensitive material containing 0.04 to 0.25 g of a polyhydric alcohol, which is a compound having a molecular weight of 150 or less per 1 g and in which hydrogen atoms of an aliphatic hydrocarbon are replaced by two or more hydroxyl groups. .