JPS62280835A - Production of silver halide photographic sensitive material having good shelf stability - Google Patents

Abstract

PURPOSE:To obtain a titled material having the stable effect of a hardener right after coating and drying till the use by storing said material for at least 24hr in an atmosphere kept at and under 18-30 deg.C and 47%-62% relative humidity RH since the end of the coating and drying of a gelatin-contg. layer until the product is packaged. CONSTITUTION:The above-mentioned material is stored for at least 24hr in the atmosphere kept at and under 18-30 deg.C and 47-62% relative humidity RH since the end of the coating and drying of the gelatin-contg. layer until the product is packaged. The amt. of the gelatin signifies the total of the amt. of the gelatin in the entire layer on the side of a base where the layer contains a compd. A, and the amt. of the compd. A signifies the amt. of the compd. A in the entire layer on the side of the base where the layer contains the compd. A. The curing effect is slow if the ratio between the amt. of the gelatin and the amt. of the compd. A is >12.0 and the resistance to sticking is deteriorated if <3.5. The curing effect is slow even in the range of (gelatin [g])/(compd. A [g]) = 3.5-1.20 if the relative humidity is <47% RH. The resistance to sticking is inferior if the relative humidity exceeds 62% RH. The compd. A is a polyhydric alcohol having >=40 deg.C m.p. and >=2 hydroxyl groups in the molecule.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel method for producing a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a method for producing a novel silver halide photographic light-sensitive material, and more specifically, a method for producing a silver halide photographic material, in which the curing action is stable for a long period of time immediately after coating and drying of the gelatin-containing layer. The present invention relates to a method for manufacturing a silver halide photographic material without failure.

C. Prior Art] -a In silver halide photographic light-sensitive materials, polyols are added to suppress fog during coating and drying, accelerate curing, strengthen pressure resistance by bending, etc., and impart antistatic properties. is being carried out.

Polyhydric alcohols that belong to a type of polyols and have at least two hydroxyl groups in their molecules and have a melting point of 40°C or higher (herein referred to as "compound A") are other than the polyhydric alcohols. Compared to polyols such as diethylene glycol and glycerin, it takes time for the curing effect of the curing agent to stabilize.

In addition, in the industry, silver halide photosensitive materials that have a gelatin-containing layer (a) are treated with a gelatin hardening agent in order to adjust the development processing speed, strengthen the physical properties of the gelatin film, and prevent elution of gelatin into the processing solution. I am using it.

It is also known to use Compound A and a gelatin hardening agent together. There are various classifications of gelatin hardening agents, but when used together with Compound A, the melting point is 40°C.
It took longer for the curing effect to become stable than when it was used in combination with a polyhydric alcohol of less than 70%. In order to stabilize the curing effect of a curing agent in a short time when used in combination with Compound A, there is a method of placing a silver halide photographic material in a high temperature or a high temperature atmosphere. However, this method has problems such as deterioration of the photographic properties of the light-sensitive materials, stickiness between the light-sensitive materials, and increased costs.

In other words, it is difficult to obtain a silver halide photosensitive material in which the effect of the hardening agent is constant over a long period of time immediately after coating and drying the gelatin-containing layer. If the curing action changes, this may undesirably lead to fluctuations in photographic properties (particularly sensitivity and maximum density) and fluctuations in image quality.

[Purpose of the invention]

The first object of the present invention is to solve the above-mentioned problems of the prior art, and to produce a silver halide photographic material which has a stable hardening effect of a hardening agent immediately after application and drying of a gelatin-containing material. We are here to provide you with a method.

A second object of the present invention is to provide a method for producing a silver halide photographic material that does not adversely affect photographic properties such as increased fog or sensitivity fluctuations.

A third object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material which has excellent adhesion resistance and is free from failures such as sticking between light-sensitive materials.

[Structure and operation of the invention]

The above object has at least one gelatin-containing layer on a support, and contains a polyhydric alcohol (compound A) having at least two hydroxyl groups in the molecule in the gelatin-containing layer and having a melting point of 40°C or higher. A silver halide photographic photosensitive material containing the following formula (1) in an amount that satisfies the following formula (1), and which is hardened with at least one type of curing agent selected from the group of compounds consisting of aldehyde compounds, active vinyl compounds, and active halogen compounds. When manufacturing the material, from the time of application and drying of the gelatin-containing layer to the time of product packaging, the material is stored for at least 24 hours in an atmosphere with a temperature of 18°C to 30°C and a relative humidity of 47% RH to 62% RH. Ru.

(1) In the above formula (1), the amount of gelatin means the total amount of gelatin in all layers of the support on the side containing compound A. Further, in the above general formula (1), the amount of compound A means the amount of compound A in the entire layer of the support on the side containing compound A.

Furthermore, in the above formula (1), (gelatin amount [g])/
If (Compound A (g) ) > 12.0, the curing effect will be slow even if the above-mentioned aldehyde compound, active vinyl compound, or active halogen compound is used as a curing agent, which is not preferable. In the above formula (1), (gelatin amount (g)
)/(Compound A Cgl )<3.5, whether the curing agent is the one used in the present invention or one other than the one used in the present invention, the curing effect is fast, but the resistance to scratching deteriorates, which is not preferable. That is, the curing action is quick, but the scratch resistance is deteriorated.

In addition, in the above formula (1), (gelatin (g))/(
Compound A (g)) = 3.5 to 12.0,
If the relative humidity is less than 47% RH, the curing effect will be slow even if the curing agent of the present invention is used, which is not preferable.
If the relative humidity exceeds 62% RH, the curing action will be quick whether the curing agent used in the present invention or a curing agent other than the present invention is used, but the scratch resistance deteriorates, which is not preferable.

Note that the gelatin-containing layer of the silver halide photographic light-sensitive material according to the present invention is, for example, a hydrophilic colloid layer, and specifically includes an emulsion layer, an intermediate layer, a retention layer, and the like.

Further, the silver halide photographic light-sensitive material obtained by the method of the present invention is, for example, composed of a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support. The silver emulsion may be coated directly on the support, or it may be coated via a hydrophilic colloid layer that does not contain the silver halide emulsion, and a protective layer may be added on top of the silver halide emulsion layer. A structure in which a hydrophilic colloid layer is coated may also be used. Further, at least one hydrophilic colloid layer containing silver halide may be provided on at least one surface of the support. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, eg high sensitivity and low sensitivity. In this case, the silver halide emulsion layer may have an intermediate layer of a hydrophilic colloid layer between itself, or an intermediate layer between the silver halide emulsion layer and the protective layer. It's okay.

The polyhydric alcohol (compound A) 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 specifically has 2 to 12 hydroxyl groups in the molecule. has 2 to 20 carbon atoms, and the hydroxyl groups are not conjugated with a conjugated chain,
In other words, alcohols that cannot form oxidized forms are preferred;
Further, the melting point is 5Q'C, but the present invention is not limited to these specific examples.

5,2.5-hexanediol 43-44
7,1,6-hexanediol 428
, 1,8-octanediol 609
．． 19-nonanediol 4510
, 1.10-decanediol 72-74
11,1.11-undecanediol 62-6
2.512,1.12-dodecanediol 7
9-79.513, 1.13-tridecanediol
76.4-76.614, 1.14-tetradecanediol 83-8515, 1.12-octadecanediol 66-6716, 1.18-octadecanediol 96-9817, cis-2,
5-dimethyl-3-\can-2,5-diol 6919
．． 2-Butyne-1,4-diol 5524
, 2,3,4-hexanetriol approx. 472
5,2,4-dimethyl-2,3,4-bencuntriol 9927, pentamethylglycerin 116-11731, erythritol 12632.0-trainto 8833, L-trainto 88-8934, ra
c-traysoto 7235,
Pentaerythritol 260-26536
, L2,3.4-pentanetetrol 10
637,2,3,4.5-hexanetetrol
16239, 1,2,5.6-hexanetetrol
9540, 1,3,4,5-hexanetetrol 8844, Adonitol
10245, D-arabitol
10246. L-arabitol
10247, rac-arabitol
10548, xylitol
93-94.549, mannitol
16450, dulcitol 1
88.5-189 The amount of the above compound 'jIJm1-50 used is not particularly limited, but is 1 g to 1 mole of halogenated compound.
The amount is preferably 100 g, more preferably 5 to 50 g. The above compounds Hiroshi 1 to 50 may be used in combination with polyols other than those used in the present invention. And the above compound 11k11~
50 is preferably added to the silver halide emulsion layer or a layer adjacent thereto. Although the timing of addition is arbitrary, it is preferably added between the end of chemical sensitization and during coating. 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).

The light-sensitive material in the present invention is hardened with at least one type of curing agent selected from the group of compounds consisting of aldehyde compounds, active vinyl compounds, and active halogen compounds.

In the silver halide photographic material according to the present invention, for example, the silver halide emulsion layer and other hydrophilic colloid layers are hardened with the above-mentioned hardening agent. These hardening agents include compounds that generate formalin as a decomposition product such as formalin, dimethylurea, and trimethylolmelamine;
Also, mucochloric acid, mucobromic acid, mucophenoxychloric acid, glyoxal, 2,3-dihydroxy-1,4
- Dioxane, 2.5-dimethoxytetrahydrofuran, aldehydes such as glutaraldehyde, vinylsulfone, N,N'-ethylenebis(vinylsulfonylacetamide), 1.3-bis(vinylsulfonyl)-2-propatol, methylene bismaleimide, 5-
Acetyl-1,3-diacryloyl-hexahydro-S
-Activated vinyl compounds such as -+-riazine, 1,3.5-triacryloyl-hexahydro-3-triazine, 1,3.5-1-rivinylsulfonyl-hexahydro-S-triazine, etc.; 2. 4-dichloro-6-hydroxy-3-)riazine
Sodium salt, 2,4-dichloro-6-nodoxy-S-
Triazine, 2,4-dichloro-6-(4-sulfoanilino)-3-triazine sodium salt, 2,4-dichloro-6-(2-sulfoethylamino)-s-triazine, N,N'-bis( Active halogen compounds such as 2-chloroethylcarbamyl)piperazine and the like can be mentioned.

Examples of particularly preferred curing agents used in the present invention include the following compounds a-i. Note that the present invention is not limited to these compounds.

a. ((412)250□
C1(=CI(2h, C(C)IZSO□C1
1=C++□)4n=4-8 The above compounds may be used alone or in combination of two or more. Moreover, the above-mentioned curing agent used in the present invention may be used in combination with a curing agent other than the above-mentioned curing agent of the present invention.

In the +M manufacturing method of the present invention, the curing agent may be added to any layer at any time, but it is most preferably added to the coating solution immediately before coating.

Specifically, the silver halide in the emulsion used in the present invention includes silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide,
Silver chloroiodobromide or the like can be used.

Here, the content of silver iodide is preferably 0.1 to 30 mol%,
In particular, it is preferably in the range of 0.5 to 10 mol%.

The average grain size of the silver halide grains is preferably 0.6 μm or more. The particle size distribution may be narrow or broad. The silver halide grains in the emulsion are regular, such as cubic, octahedral, and dodecahedral.
It may have a regular crystal shape, or it may have an irregular crystal shape such as spherical, plate-like, potato-like, etc., or it may have a composite shape of these crystal shapes.

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, Glafkid
es, Chimie et Physique (Chimie et Physique)
Photographique % Pau1Mo
nte1, 1967), G, H, Duffin
Author, Photographic Emulsion Chemistry (
Photo to graphic Emulsion C
hemistry), The Focal Pres.
s, 1966), ν, L, Zelikman
Making and Coating Photographic Ink Emulsions by et al.
Coating Photo-graphic Em
ulsion, published by The Focal Press,
(1964) et al. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, a combination thereof, etc. .

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 in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrord-Doublejet method can also be used.

According to this Chondrold double jet 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 hole types formed separately may be used in combination.

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 soluble salts of the emulsion used in the present invention are usually removed after precipitation or physical ripening, and the means for this purpose may be the Tardel water washing method, which involves gelatinizing gelatin. Utilizing inorganic salts 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 gelatin, etc.) A sedimentation method (flocculation) 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 it can be used as is as a so-called primitive emulsion, it is usually chemically sensitized.

For chemical sensitization, the above-mentioned book by Glafkicles or Zelikman et al.
er ed.
Die Grundlagen der Photog
Raphischen Prozessemit Si
lberhalogeniden, Akademis
che Verlags-gesellschaft,
(1968) can be used.

In other words, sulfur sensitization using a sulfur-containing compound or activated gelatin that can react with negative ions, reduction sensitization using a reducing substance, noble metal aggravation using gold or other noble metal compounds, etc. may be used alone or in combination. Can be done. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used,
Specific examples thereof include U.S. Pat.
No. 728,668 and No. 3.656.955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. No. 974, 2,
No. 518,698, No. 2,983.609, No. 2,983
, No. 610, No. 2,694,637.

For noble metal aggravation, in addition to gold complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used. Specific examples thereof include U.S. Pat. No. 060, British Patent No. 618,061, etc.

Various hydrophilic colloids can be used as binders in the silver halide photographic material according to 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 colloid, a hydrophobic colloid such as a dispersed polymerized vinyl compound, especially one which increases the dimensional stability of the silver halide photographic light-sensitive material, can be contained. 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. Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), peterocyclic 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 oxazolinthione, azaindenes such as tetraazaindenes (particularly 4-hydroxy substituted (1,3,3
a.

7) Many 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 K0Mees, The Theory of the Photographic Ink Process (Th
e Theory of the Photography
hic Processs, 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.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.8 to 7.
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within the above range of 5.8 to 7.5. If the pH is less than 5.8, the progress of hardening will be slow, which is undesirable, and if the pH is greater than 7.5, it will often have an adverse effect on photographic performance, which is undesirable.

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

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 alkyl ethers, polyalkylene glycols) Nonionic interfaces such as alkylamides or amides, polyethicine oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator, alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurate sulfosuccinate, sulfonate Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as alkyl polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphate esters; amino acids; , aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amphoteric surfactants such as amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, complex compounds such as pyridinium, imidazolium, etc. Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The silver halide photographic material according to 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, ab dyes, and the like. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to 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.
912, Japanese Patent Publication No. 45-5331, etc., may be included.

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 material according to 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, hemioxonol dyes, and the like. 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, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indole nucleus , benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, penduthiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. 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 aggravating dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. In particular, it is advantageous to use a dye concentration that does not substantially reduce the aperture sensitivity of the silver halide emulsion. A concentration of from about 1, OXl0-' to about 5X10-' moles of sensitizing dye per mole of silver halide is preferred, and in particular from about 4X10-' to 2XIO-' moles of sensitizing dye per mole of silver halide. preferable.

The silver halide emulsion used in the present invention contains 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. May include. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to the ion. 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 coloring coupler, various open chain ketomethylene couplers can be used. Among these, benzoylacetanilide-based and pivaloylacetanilide-based compounds are particularly important.

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 according to 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
Alternatively, a smoothing agent or the like may be added.

As an example of a mantle agent, an appropriate particle size (particle size of 0.3 to 5 μm) is used.
or silver halide or an organic compound such as a water-dispersible vinyl polymer such as polymethyl methacrylate (preferably at least twice the thickness of the protective layer, particularly preferably at least 4 times the thickness of the protective layer) Inorganic compounds such as barium strontium sulfate and the like are preferably used. Smoothing agents are useful in preventing adhesion failure similar to matting agents, and are particularly effective in improving frictional properties related to camera compatibility during shooting or projection of motion picture film; a specific example is liquid paraffin. , waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, polyalkylpolysiloxanes, polynuclear polysiloxanes, polyalkylarylpolysiloxanes, or alkylene oxide addition derivatives thereof. Silicones such as the like are preferably used.

The silver halide photographic material obtained by the present invention includes:
In addition, if necessary, anti-halation layer, intermediate layer,
A filter layer or the like can be provided.

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

Various other additives may be used in the silver halide photographic material used in the present invention, if necessary. For example, dyes, development accelerators, optical brighteners, color antifoggants,
UV absorbers, etc. Specifically, research disclosure (RESEARCHDISCLO3UII)
E) No. 176, pages 28-30 cRo = 17643
．． (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 carrying out the silver halide photographic material of the present invention, for example, 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. (e.g. polyethylene, polypropylene, ethylene/butene copolymer)
paper coated or laminated with etc. 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 undercoating process is based on JP-A-52
Preferred are the treatments described in JP-A-104913, JP-A No. 59-18949, JP-A No. 59-19940, and JP-A No. 59-19941.

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 light-sensitive material according to 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, it is used in X-ray photographic materials, squirrel type photographic materials, black and white negative photographic materials, color negative photographic materials, color paper photographic materials, and the like.

It can also be used in diffusion transfer photosensitive materials, color diffusion transfer photosensitive materials, etc., which produce positive images 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 according to the present invention, for example, Research Disclosure (Research Disclosure)
Any of various methods and various treatment liquids, such as those described in J. Ch. Disclosure, No. 176, pages 28-30 (RD-17643), can be applied. This photo processing can be done depending on the purpose. It may be either a photographic process that forms a reverse image (black and white photographic process) or a photographic process that forms a dye image (color photographic process). The processing temperature is usually selected between 18°C and 50°C, but it may also be below 18°C or above 50°C.

For example, the developer used in black-and-white photographic processing can contain a developing agent. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone),
Aminophenols (for example, N-methyl-〇-aminophenol) and the like can be used alone or in combination.

The silver halide photographic material of the present invention may be photographically processed using a developer containing indazoles as a silver halide solvent as described in Japanese Patent Application No. 155489/1982. 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. Developing solutions generally contain various preservatives, alkaline agents, and pHJ.
Contains a buffering agent, anti-fogging agent, etc., and may further contain a solubilizing agent, a color toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, etc. as required. .

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" development processing is a development process in which dihydroxybenzenes are usually used as a developing agent and a low sulfite ion temperature is used for photographic reproduction of line images or halftone images with halftone dots. A special type of development process that uses a developing agent In the photosensitive material,
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 the composition used in -a 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 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, 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., by F. A. Mason: Photographic Pro-ceeding Chemistry, Focal Press.
ssing Chemistry, Focal Pr
ess), 1966, pp. 226-229, US Patent 2
, No. 193,015, No. 2,592,364, JP-A-48-64933, etc. may be used.

The color developer can 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. etc. may also be included.

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. Bleach agents include Fe″3, CO゛4,
Compounds of polyvalent metals such as Cr'' and 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
In addition to the bleach accelerators described in Japanese Patent Publication No. 45-8836 and the thioether compounds described in JP-A No. 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 deterioration, 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.

As for the exposure time, in addition to normal exposure of 1/1000 to 100 seconds, short-time exposure of 1/10' to 1/10' of a xenon flash, cathode ray tube, or laser light can be applied.

〔Example〕

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 An inner core of Hayabusa-dispersed silver chloroiodobromide containing 2 mol% of iodine and 0.2 mol% of chlorine with an average grain size of 0.18 μm, and a ratio of 40 mol% of iodine and 60 mol% of bromine on the outside thereof. A silver iodobromide layer was formed and grown to a grain size of 0.5 μm, and then a silver iodobromide layer was grown to a grain size of 0.85 μm at a ratio of 1 mol% iodine and 99 mol% bromine, giving it a slightly rounded shape. Thus, dodecahedral silver halide grains were obtained.

Chloroauric acid salts, rhodanammonium, sodium thiosulfate, and thiourea compounds were added to these particles, and the particles were chemically ripened.

The incidence of compound A per 70 g of this particle is 20.30,44,
Comparative Compound B (diethylene glycol), Compound C (glycerin), Compound D (1,4-butanediol) or Comparative Compound E (1,2,6-hexanetriol) was added to lime in the amounts shown in Table 1. 30g processed gelatin
In addition, a stabilizer and a thickener were added to prepare an emulsion preparation. At this time, the pI of the emulsion solution was 6.52 at 40°C.

This emulsion preparation solution and the protective layer solution described below were combined; the emulsion solution had a silver content of 4.8 g/m, and the protective layer solution had a gelatin content of 1.8 g/m.
Coating speed 150m/m to give og/m
The samples were simultaneously coated on a polyethylene terephthalate support at 2 min and dried for 2 minutes and 30 seconds to obtain samples 1lhl to 24 in Table 1.

Protective layer liquid〉 (A) ・Gelatin 100g・C
1□Hzs-0(CHz-CH□oL.-H2,5gC
H,-COOCI. 1(21 -NaO:+5-CI(-COOCsFl+ 1
2.0 g・Polyvinylpyrrolidone (average molecular weight: 115,000) g・Polymethyl acrylate particles with an average particle size of 3.5 μm
3g Ludox AM
(manufactured by DuPont) as the solid component of the total binder.
Add 0.5 g of exemplified curing agent e and water to give a total weight of 21 (KIN liquid) p'H is 40'C, 03).

, a continuous roller conveyance type automatic system that can perform the entire process of developing solution, fixing, washing, and drying after white exposure is performed using a KS-1 type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.) based on the IS method. Processed with a developing machine. The developer used is as follows.

Developer formulation (Development time: 35°C, 30 seconds) Sensitometry was performed on each sample obtained in this way,
The photographic properties obtained are shown in Table 1. Note that the sensitivity shown in the table is for Sample No. 6 according to the present invention at 25° C. 55% RH.
This is a relative sensitivity value with the sensitivity of the 30-day sample as 100.

In addition, as a measure of gelatin hardening degree, the maximum density of the sample obtained by the above sensitometry method and the scratch resistance test after immersing the sample in the above developer (25°C for 1 minute) were conducted as follows. Ta. In addition, the scratch resistance of the film was evaluated as follows.

After the sample was immersed in a developer, the swelling layer was scratched with a 0.2R sapphire needle under a continuously changing load.

The strength (hardness) was expressed as the load at which scratches began.

Heat oven test for aging (stick resistance test) 25℃,
The same samples that had been conditioned for 12 hours under 55% RHO were stacked together and a load was applied so that a pressure of 20 g/c++I was applied, the film was shielded, and heat treated by placing it in a thermostat at 55 °C for 4 days to bond the films together. The degree of stickiness was evaluated on a four-grade scale from A to D as shown below.

A: No footpecker at all B: Footpecker area less than 5% C: Footpeke area less than 15% D: Footpeke area 15% or more From Table 1, samples 1'h2.3.6.7°10 and 11 according to the present invention are All of them were found to have a stable curing effect over a long period of time immediately after application, and to have good scratch resistance.

Example 2 Exemplary Compound C1 Exemplary Compound G or the comparative gelatin hardeners A, Q and C below were used, and the amount of these gelatin hardeners added was 30°C in an atmosphere of 955% RH at 25°C.
Samples 1 to 27 in Table 2 were obtained in an amount that gave a maximum concentration of 3.40 when stored for 1 day.

0-C1h These samples were conditioned for 12 hours in an atmosphere with the temperature and humidity shown in Table 2, then sealed and sealed airtight, and heated at 25°C.
After being left at 55% R'H for 24 hours and 30 days, sensitometry was performed in the same manner as in Example 1, and the scratch resistance was evaluated in the same manner as in Example 1. In addition, the scratch resistance is the second
After adjusting the humidity as shown in the table, add 50g/c to the encapsulated film.
After 30 days of applying ot pressure, evaluation was made.

The evaluation results are shown in Table 2. From Table 2, the sample +1.7.8.12 according to the present invention shows that after 24 hours, 3
It was found that it had similar sensitometric performance and scratch resistance after 0 days. In addition, the sensitivity after 30 days,
It can be seen that the scratch resistance is also excellent.

As is clear from the above-mentioned Examples 1 and 2, the silver halide photographic material produced according to the present invention has a stable photographic performance after one day of coating and drying because the curing action progresses quickly. It was also found that the photographic performance remained stable even after more than one year had passed.Q According to the present invention, the hardening action of the gelatin hardening agent is further promoted to improve photographic performance, scratch resistance, and stickiness resistance from the initial stage. Silver halide photographic materials with improved properties can be produced. The photosensitive material obtained according to the present invention does not deteriorate photographic performance even if the packaged product is exposed to high temperatures (30 to 40° C.) for a long time during transportation or storage, and does not cause any sticking failure.

〔Effect of the invention〕

As described above, according to the present invention, coating a gelatin layer,
It is possible to produce a silver halide photographic material in which the hardening agent has a stable hardening effect immediately after drying until the time of use.

Further, according to the present invention, a silver halide photographic light-sensitive material having good photographic properties such as increased Fog and sensitivity fluctuation can be produced.

Furthermore, according to the present invention, it is possible to produce a silver halide photographic light-sensitive material that does not suffer from problems such as sticking between light-sensitive materials.

Claims (1)

[Scope of Claims] 1. A polyhydric alcohol having at least one gelatin-containing layer on a support, having at least two hydroxyl groups in the molecule in the gelatin-containing layer, and having a melting point of 40°C or higher ( A halogenated compound containing compound A) in an amount satisfying the following formula (1) and hardened with at least one type of curing agent selected from the group of compounds consisting of aldehyde compounds, active vinyl compounds, and active halogen compounds. A method for producing a silver photographic material, the temperature being 18°C to 30°C and the relative humidity 4 from the time of application and drying of the gelatin-containing layer to the time of product packaging.
A method for producing a silver halide photographic material, which comprises storing the material in an atmosphere of 7% RH to 62% RH for at least 24 hours. 3.5≦Amount of gelatin [g]/Amount of compound A [g]≦12
．． 0