JPS62131248A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To inhibit the rot of various coating solns., to improve the productivity and to reduce the load of facilities including storage equipment by regulating the calcium content in gelatin as hydrophilic colloid to <=1,000ppm. CONSTITUTION:Gelatin contg. <=1,000ppm calcium is obtd. by properly combining the selection of starting materials with the selection of conditions during production and the adoption of ion exchange or other treatment. Various trace constituents are present in the gelatin besides calcium and some of them affect the propagation of microorganisms, so it is necessary to observe well constituents which accelerate the propagation. For example, the amount of phosphoric acid is preferably restricted to <=200ppm (expressed in terms of PO4).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material), and in particular to a method for preservative treatment of a hydrophilic colloid solution used as a binding material for a light-sensitive material. Regarding the method.

[Prior art]

Generally, a light-sensitive material is formed by coating a support with at least an IWi photosensitive emulsion layer, and if necessary, coating a subbing layer, an intermediate layer, and other photographic constituent layers. Hydrophilic colloids used as binding agents for these photographic constituent layers include gelatin, colloidal albumin, agar, gum arabic, alginic acid,
Cellulose derivatives such as hydrolyzed cellulose acetite, carboquine methyl cellulose, hydroxyethyl cellulose, methyl cellulose, synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, polyN, N-methylacrylamide, Poly N-vinylpyrrolidone, US Patent 3
, No. 847,620, No. 3,655,389, No. 3,
341゜332, 3,615.424, 3,8
Water-soluble polymers such as those described in U.S. Pat. No. 60,428, U.S. Pat.
Gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and heptadated gelatin as described in U.S. Pat. No. 53, U.S. Pat.
Acrylic acid (as described in No. 31,767 etc.)
ester), methacrylic acid (ester), acrylonitrile, etc., which can be polymerized with ethylene, gelatin, and gelatin. These binders can be used as a compatible mixture of two or more, if desired.

It is known that hydrophilic colloids used as paint in photosensitive materials are easily affected by microorganisms such as bacteria, yeast, and mold. In particular, when a photographic hydrophilic colloid solution is coated on a support, the influence of microorganisms becomes more serious because the coating is carried out at a stagnant temperature suitable for microbial growth.

For example, when a hydrophilic colloid rots or decomposes due to microorganisms, the viscosity of the coating solution decreases, the strength of the applied film decreases, and bacteria etc. aggregate to form small clumps, causing defects such as comments. It may not be possible to obtain a uniform coating film, or the metabolites of microorganisms may have an adverse photographic effect.

Hydrophilic colloids used in photosensitive materials, yeast,
In order to prevent such defects caused by mold and the like, it is known to add bactericides and anti-fungal agents to photosensitive materials.

In general, preservatives or anti-corrosion agents for such purposes include, for example, 7-ethyl, 7-ethymol, chloro-7ene, nochloro-7ene, bromochloro-7ene, 2,2'-nohydroxy- 5゜5'-nochlorodiphenylmo/sulfite, 2,4゜4'-trichloro-
2'-hydroxydiphenyl ether, 3,4.5-
) Aromatic hydroxy compounds or their salts such as ribromosalicylanilide, 4-rhohequinluresorcin, or carboxylic acids or their esters such as benzoic acid, monobromoacetic acid ester, p-hydroxybenzoic acid ester, sorbic acid, or Amines such as xamethylenetetramine, alkylquanisine, nitromethylbennorethylenediamine, fusulfides such as tetramethylthiuramnosulfide, 2-mercaptobenzothiazole, 2-(4-thiazolyl)-bencyimiguzole, 2-methoxy Nitrogen-containing heterocyclic compounds such as carbonylamide 7-penziimiguzole, or organic mercury compounds such as phenylmercuric acetate, phenylpropionate, and phenyloleate, or antibiotics such as neomycin, kanamycin, polymycin, streptomycin, and flamycin. Substances are known, and some of these are also known for use in photography. However, these substances may not be effective unless added in large quantities to hydrophilic colloids, may be harmful to living organisms, may be effective only against certain bacteria, or may be harmful to photographs. In many cases, the bactericidal effect is insufficient due to sterilization or interaction with other photographic additives. For example, the most often used 7
Seven alcohols such as rutimol do not exhibit a sufficient preservative effect unless added in an amount of 2% by weight or more based on the hydrophilic colloid. Moreover, 7-el has a preservative effect against bacteria, but it has a preservative effect against mold and yeast.
It has little anti-inflammatory effect and is highly toxic to living organisms.

Heterocyclic compounds such as benzothiazoles may also exhibit photographically harmful effects, such as desensitizing effects. Organic mercury compounds are effective against mold fa+1'-atk
mtsuV'El+++↓hkIn, A#Il-, Tono rLj Akira-fan--4 first 1. Yee is harmful. Antibiotics such as neomycin and kanamycin are effective against bacteria, but not against mold and yeast.

If a large amount of disinfectant is used, it will adversely affect the physical properties of the coating solution, for example, cause agglomeration of the binder, and also deteriorate the photographic properties of the finished light-sensitive material.

Therefore, it is desirable to use as little fungicide as possible or not to use it at all.

On the other hand, when gelatin is used as one of the hydrophilic colloids, a hardening agent is often added for the purpose of improving the processing suitability of the photosensitive material.

Many hardening agents exhibit a preservative effect when a hydrophilic colloid solution is added and the solution is stagnant; for example, formalin has a strong preservative effect against bacteria.

However, for some types of photosensitive materials, for quality reasons, it is not possible to add the hardener to the hydrophilic colloid solution and let it stagnate. Addition method is used. The second method is called in-line addition in this field. In this case, stop′/
The antiseptic effect of the hardening agent on the colloidal solution at the time of m cannot be expected, and therefore antiseptic measures are necessary.

[Purpose of the invention]

A first object of the present invention is to provide a method for producing a photosensitive material using a novel method for preserving a hydrophilic colloid solution used for coating a photographic constituent layer of a photosensitive material containing a hydrophilic colloid. .

The second object is to provide a method for producing a photosensitive material using a preservative method for hydrophilic colloids that does not have any adverse effect on photographic performance (sensitivity, fogging, graininess, sharpness, etc.).

[Structure of the invention]

As a result of various studies, the present inventors have found that the purpose of the present invention is to:
In a method for manufacturing a photosensitive material in which a hardening agent having preservative properties is added in-line to hydrophilic colloid dissolution, the calcium content of gelatin, which is the hydrophilic colloid, is 10001).
It has been found that this can be achieved by keeping the temperature below 11 tfl.

The present invention will be explained in more detail below.

In the present invention, the hydrophilic colloid for light-sensitive materials refers to the gelatin contained in the coating liquid used for coating various photographic constituent layers of light-sensitive materials, that is, the gelatin coated at the beginning of the description of the prior art. Natural hydrophilic polymer primary V derivatives such as agar, colloidal albumin, gelatin, cellulose derivatives, synthetic hydrophilic polymers such as polyvinyl alcohol, sols of delta-shaped parent wood colloids and their dry glues, and coatings. Refers to compositions such as coating liquids that are in the preparation process, storage, or formulation process of solutions or dispersions of various compounds that are soluble, sparingly soluble, or insoluble in water, and are used in the preparation of liquids. Emulsions, couplers,
These include dispersions such as matting agents, surfactant solutions, dye solutions, and various additives. The conditions that must be met as a preservative method for hydrophilic colloids for photosensitive materials are (1) no effect on photographic performance such as desensitization, fogging, graininess, sharpness, etc., and (2) development, desilvering, and reversibility. It is desirable that there be no effect on processing performance such as color, (3) no effect on the environmental ecosystem, and (4) no adverse effect on the human body. The present invention substantially satisfies these requirements.

In the present invention, a hardening agent having antiseptic properties refers to a hardening agent having the effect of suppressing the growth of microorganisms when added to a hydrophilic colloid solution as described above.

The presence or absence of antiseptic properties can be determined by the following method.

(Preservative test method) Gelatin aqueous solution containing 6g of gelatin Loom! l to 3
Prepare a hardener and add a hardening agent to it.
Add each mg. Pseudo+nona in this sample
After inoculating 10" of S. aeruginosa bacteria, culture with shaking at 37°C, and check the number of bacteria in each sample every 3.6.24 hours.Furthermore, add 107 of the above bacteria to another set of samples.
Inoculate them individually and test in the same way.

The number of bacteria in the two sets of samples described above is compared with the sample to which no hardening agent is added, and when the number of bacteria is smaller than the reference sample, it is determined that there is a preservative effect.

The above-mentioned Pseudomonas aeruginosa bacterium can be obtained, for example, from the Institute of Applied Microbiology, University of Tokyo. Nutrieut broLh is used to measure the number of bacteria.
Use the dilution plate method using an agar medium.

Examples of hardening agents that exhibit antiseptic effects according to such test methods include the following compounds.

Formaldehyde, glyoxal, glutaraldehyde, mucochloric acid, mucobromic acid, 3-hydroxymethyl-4,4-nomethylhyguntoin, 1,2-bis(vinylsulfonyl)ethane, hexahydro-1,3゜5-
Tris(2-hydroxyethyl)-S-trianone, 2
．． 4-fuchloro6-hydroxy-5-)rianone.

In the present invention, stagnation of the hydrophilic colloid solution means that 2 hours or more elapses after solution preparation and before application. During this opening, the solution itself may be in any state of being stationary, stirring, or being transferred.

In general, in hydrophilic colloid solutions such as gelatin, under the temperature conditions used to manufacture photosensitive materials, the number of microorganisms doubles every 20 to 30 minutes. Actual damage begins to occur. To avoid this, it is sufficient to apply the solution approximately one hour after preparation, but this is disadvantageous in terms of equipment and cost.

The calcium content in gelatin was measured according to the method described in Photographic Gelatin Testing Method (abbreviated as Bagii method), 5th edition, 24 Shin (1982) established by the Joint Council for Photographic Gelatin Testing Methods.

Calcium in gelatin is obtained from polished rice as a raw material, but in order to obtain gelatin having the calcium content of the present invention, selection of raw materials, selection of manufacturing conditions, 7-ion exchange treatment, etc. may be appropriately combined.

The gelatin according to the present invention has a calcium content of 1000 pH.
It is necessary that it is less than or equal to ln. Moreover, when several gelatin melts are mixed and used, the calcium content is expressed as a weighted average value.

In addition to calcium, gelatin contains many other trace components, some of which affect the growth of microorganisms. Therefore, it is necessary to be careful about ingredients that promote proliferation. For example, phosphoric acid (PO) is 20
01) I) It is desirable to control it to below m.

The present invention aims to obtain the preservative effect of hydrophilic colloid without using a disinfectant, but considering the photographic performance and the influence on the environment and ecosystem, a good disinfectant, such as a British patent, is used. Compounds described in No. 90584 can also be used in combination.

The photosensitive material using the wood-philic Colloy V to which the preservative method of the present invention is applied will be described in more detail below.

The silver halide emulsion of the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

The silver halide grains used in the a Y ffi emulsion may be those obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH in the mixing pot and/or 1) Δg. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, the halogen composition of the particles is changed using the Compernoyon method.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, ilinium salts (including complex salts), rhodium salts (including complex salts), and iron salts. It is possible to add metal ions using at least one kind selected from (including complex salts) and to contain these eight groups inside the particles and/or on the particle surface. By creating an atmosphere of
Reduction sensitizing nuclei can be attached to the interior of the particles and/or the surface of the particles.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research Disclosure + D 1
(hereinafter abbreviated as RD) No. 17643 n
This can be done based on the method described in Section 1.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/'shell grains in which the silver halide composition differs between the inside and surface layer of the grain.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the 1001 plane to the 1lll1 plane can be used, and the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

Silver halide emulsions may have a wide grain size distribution (referred to as polydisperse emulsions), or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. It is called a dispersed emulsion.The monodispersed emulsion referred to here refers to one whose value when the standard wall deviation of the grain size distribution is divided by the average grain size is 0.20 or less.The grain size is spherical. In the case of silver halide, the diameter is shown, and in the case of grains having a shape other than spherical, the diameter is shown when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. Sensitizing dyes may be used alone, but 2!91
The above may be used in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as anti-capri agents or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. can.

The hardening agent can be added to the processing solution in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section 2, A.

For the purpose of improving dimensional stability, etc., a dispersion (Latinx) of a water-insoluble or sparingly soluble synthetic polymer may be contained in the V layer of a photosensitive material. can.

The emulsion layer of the light-sensitive material is subjected to a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, 1)-7 unilene diamine derivative, ami/7 ether/-el derivative, etc.) during color development processing. A dye-forming coupler is used that performs this process to form a dye. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are tetraisotropic, in which four molecules of silver ions need to be reduced in order to form one molecule of dye, only two molecules of silver ions need to be reduced. Either 2nd class is fine. Dye-forming couplers have the effect of color correction.By coupling the coupler with the oxidized form of the developing agent, it can be used as a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, and a toning agent. Compounds that release photographically useful 7-ragments such as agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. [) An IRR compound (I') which undergoes a coupling reaction with an oxidized developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used as the IR coupler.

The DIR couplers and DIR compounds used include those in which the inhibitor is directly attached to the camping position and those in which the inhibitor is attached at the 2-position.
Intra-molecular nucleophilic reaction, which is bonded to the coupling position via a valent group and released by the coupling reaction,
These include compounds in which the inhibitor is bonded such that it is released by an intramolecular electron transfer reaction or the like (referred to as a timing DIR coupler and a timing I R compound). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. Colorless couplers (vi!, also referred to as resultant couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination with dye-forming couplers.

As the yellow dye-forming coupler, known acylacetanilide couplers are preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, open-chain azilacedonitrile couplers, ingzolone couplers, and the like can be used.

As the cyan dye-forming coupler, a 7-l or 7-tol coupler is generally used.

It is necessary to adsorb/ri on the silver halide crystal surface - Dye-forming couplers, colored couplers, DIR couplers,
Among DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler.

Oil-in-water type? The L-forming dispersion method can be applied using a conventionally known method for dispersing hydrophobic additives such as couplers, and usually a high boiling point organic solvent with a boiling point of about 150"C or higher is mixed with a low boiling point and/or water-soluble organic solvent as necessary. Dissolve using a solvent and emulsify using a dispersion device such as a stirrer, homogenizer, colloid mill, 70-knot mixer, ultrasonic device, etc. using a W surfactant in a hydrophilic binder such as an aqueous gelatin solution. After that, it may be added to the desired hydrophilic colloid liquid.

A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion.

Examples of high boiling point solvents include 7-ethyl H4 which does not react with the oxidized form of the developing agent, 7-tar acid alkyl ester, phosphoric acid ester, citric acid ester, AmQ buoyant ester, alkyl amide, dimethyl fatty acid, and trimesine. An organic solvent such as an acid ester is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of low boiling point substantially water-insoluble tIi solvents include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform,
Examples of water-soluble organic solvents include carbon tetrachloride, nitromethane, nitroethane, and benzene. Examples of water-soluble organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, and dimethylformamide. , dimethyl sulfoxide, hexamethylphosphorin triamide, diethylene glycol moaphenyl ether, 7-ethyl-oxyethanol and the like.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, /
Ionic surfactants, cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color anti-capri agent may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsion layers and included in the coating.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD 17643 No.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of photosensitive materials due to friction, etc., and to prevent deterioration of images due to UV exposure. Good too.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD176.
The compound is a compound described in Section XXI, Section B-0 of No. 43, and the development retardant is a compound described in Section XXI, Section E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of photosensitive materials increases sensitivity, increases contrast,
Or, for the purpose of accelerating development, polyalkylene oxide or its derivatives such as ethers, esters, and amines, 1,000-onythyl compounds, thiomorpholines, quaternary ammonium compounds,
It may also contain urethane derivatives, urea derivatives, imiguzol derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as fluorescence sensitizers are described in section V of RD 17643.

The photosensitive material can be provided with a filter layer, an antihalation layer, and an auxiliary layer of an antiirradiation layer.

Im l+ times 111 in these layers and/or in the emulsion layer
kn, i [! Yuriyuukikine J t:L, h-whip 0 Higashi eggplant A, 4.1 or a dye to be bleached may be contained.

Examples of such dyes include oquin/ole dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added to prevent photosensitive materials from sticking to each other.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 X1ll.

The halogenated kite emulsion layer and/or hydrophilic colloid layer of photosensitive materials have various properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing after-shot, and photographic properties (accelerating development, hardening, and sensitization. !!?) Various surfactants can be used for the purpose of improvement.

The support used in the photosensitive material of the present invention includes an α-olefin polymer (for example, polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, plastics, metals, ceramics, etc.

The hydrophilic floid layer of the photosensitive material can be applied directly or after applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, or to improve the adhesion, antistatic properties, dimensional stability, and abrasion resistance of the support surface. The coating may be coated via one or more subbing layers to improve properties such as hardness, hardness, antihalation properties, clamping properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, for materials such as hardwood cutting, which are reactive and may cause delification before application by adding additives to the coating solution, mix it on the surface to be coated using a static mixer etc. It is preferable to do so.

As a coating method, extra roots coating and curtain coating, which allow two or more types of waste to be coated at the same time, are particularly useful, but depending on the purpose, Bakent coating may also be used. Further, the coating speed can be arbitrarily selected.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode #l tube flying spots, various lasers, luminescent light, electron beams, X-rays, Any known light source can be used, including those emitted from phosphors excited by gamma rays, a@, and the like.

The three critical times include not only exposure times of 1 millisecond to 1 second, which are normally used in cameras, but also exposures shorter than 1 microsecond, such as exposures of 100 fps to 1 microsecond using a cathode ray tube or xenon flash lamp. Exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

Any known method can be used for developing the photosensitive material of the present invention. This development process is a process that forms a silver image depending on the purpose. (black and white development processing) or development processing that forms a color image. If an image is created by the reversal method, a black negative development process is first performed, and then a color development process is performed by applying white exposure or processing with a bath containing a fogging agent. It is also possible to use a silver pigment (white pigment) in which a dye is contained in the light-sensitive material, a black-and-white development process is performed after exposure to form a silver image, and this is used as a bleaching catalyst to bleach the dye.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 After heating gelatin containing calcium-containing 52 old
It was dissolved in water to make 200 mQ of a 5% gelatin aqueous solution.

At this time, calcium chloride was added in varying amounts to prepare six types of solutions with different carunium contents. Divide these into two,
One group has PSeudomona Saerugino.
sa(^)・Δcinetobacter for other groups
amitratus (B) and 12 types of samples (N
o, 1 to 12) were created. Each test sample was incubated with shaking at 37°C, and sterilization in the solution was measured after 3 and 6 hours using the dilution lithography method described above. The results are shown in Table 1.

Margin table below 1 From Table 1, samples according to the present invention (No. 1 to 4.7 to 10
) shows that bacterial growth is slow.

Example 2 High-sensitivity silver iodobromide emulsion for X-ray containing 0.5 mol% of fi iodide (containing 6% gelatin) 10 (calcium chloride was added to hQ as shown in Table 2, and a portion was stagnated for 3 hours. Formalin was added in-line as a hardening agent and coated on a polyethylene terephthalate support to prepare a sample for sensitometry.
One species of bacteria belonging to the genus rol+acLer was inoculated, cultured with shaking at 37°C, and the number of bacteria was determined after 3 hours.

The sensitometry was performed using a KS-] type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) after exposure, development with the following developer (40''C, 130 seconds), fixing, and washing with water.

[Development'e composition]

Table 2 shows the bacterial counts and sensitometry results.

Table 2 However, the sensitivity is expressed as a relative sensitivity with the sensitivity of sample No. 13 as 100.

As is clear from Table 2, the sample according to the present invention (NO01
It can be seen that samples 3 to 15) exhibit the effect of inhibiting bacterial growth without adversely affecting photographic performance.

Example 3 A sample of a highly sensitive multilayer color negative photosensitive material (No. 17-
20) was manufactured.

f: tsIM: antihalation layer containing black colloidal silver (dry film thickness lμ).

2nd Nj: Gelatin intermediate layer containing 2,5-not-t-octylhydroquinone (dry film thickness 1μ).

3rd layer: Red-sensitive emulsion layer l-Hydroxy-N-[γ-(2,4-not-7mil7eth/xy)butyl]-2-su7tamide6 as cyan coupler per mole of silver halide .8 x 10-2 mol, 1-hydroxy-N-[δ-
(2,4- to 1-7 mil 727 xy)]-4-(
2-ethoxycarbonylphenylazo)-2-su7tamide 1,7X 10-2 mol, 2-(1-phenyl-5-tetrazolylthio)-4 as a development inhibitor-releasing substance
-(2,4-not-7 milphenoxyacetamide)
- Red-sensitive silver iodobromide emulsion layer containing 10-' mol of 1-indanone 4X (silver iodobromide emulsion containing 8 mol % silver iodide,
Dry film I￥-6μ).

4th layer: middle layer Same as the second scrap.

5th layer: I-(2,4,6-trichloro)phenyl-3-C3 as magenta coupler per mole of silver halide
-(2,4-di-t-7-milphenoxy)acetamide]benzamide 5-pyrazolone 5.8X 10-2 mol, as colored coupler 1-(2,4,6-)lychlorphenyl)-3-(3- (octatecenylsuccinimide)-2-chloro]anilide-4-(γ-su7tylazo)-5-pyrazolone 1.7X 10-2 mol, and 2-(1-phenyl -5-tetrazolylthio)-4-(2,4-not-t-amylphenoxyacetamide)-1-indanone 7X
A green-sensitive, low-sensitivity silver iodobromide emulsion layer containing 10-2 moles of silver iodide (silver iodobromide containing 8 moles of silver iodide!?6), polished, dried V thickness 3.5
μ). 6th layer: The same compounds as the f55 M magenta coupler, colored coupler and development inhibitor-releasing substance were used in amounts of 1.1X 10-2 mol, 5X 10-3 mol, and 2X 10-' mol, respectively, per mol of silver halide. Highly sensitive silver iodobromide, containing green sensitivity! ? L layer removal (silver iodobromide emulsion containing 16 mol% iodide, dry film FI-2, 5μ).

7th layer: middle layer Same as second layer.

3rd layer: yellow filter one layer yellow gelatin N containing colloidal silver and V2.5-1 octyl hydroquinone (dry film thickness 1μ).

9th layer: blue-sensitive emulsion layer 1 mol of silver halide I), yellow coupler and shite α
-pivaloyl-α-(1-bentrue-2,4-nooxyimigzolinon-3-yl-2'-chloro-5-[γ-
(2,4-not-t-amyl7eth-7xy)butyramide]
Acetanilide 2.5X IO-'mol, ω-promo ω-(1-7enyl-5-
4-sensitive silver iodobromide emulsion layer containing 5X 10-' moles of (tetrazolylthio)-4-lauroylamide acet7ene (silver iodobromide emulsion containing 7 mol% silver iodide, dry V thickness 7μ)
).

10th scrap: protective layer Gelatin layer (dry film I!f, 1μ).

However, the gelatin used in the 2nd, 4.7th and 10th layers was selected from those having the calcium content shown in Table 3.

In addition, each layer is coated with coating liquid i11! After being stagnant for 3 hours after production,
It was manufactured by adding 1,2-bis(vinylsulfonyl)ethane in-line as a hard chewing agent.

These samples (Nos. 17 to 20) were subjected to wedge exposure through a green filter, and then subjected to the following development treatment.

[Color developer j11]

Add i to get IQ, 1:+ II to 10.0, y4
Arrange.

[Bleach solution composition]

[Fixer composition] [Stable bath composition] Each developed sample (sensitometry was performed under green light).

In addition, after preparing the second and tenth layers, one net
After inoculating one strain of the bacLer genus, it was cultured with shaking at 37°C for 3 hours, and the number of bacteria was determined.

The results of sensitometry and bacterial count are shown in Table 3. However, the sensitivity was expressed as a relative sensitivity with the sensitivity of sample No. 17 as 100.

From Table 3 below, it can be seen that the samples of the present invention suppressed the growth of bacteria and had good photographic performance.

〔Effect of the invention〕

By implementing the present invention, the purpose of the invention can be fully achieved, and industrial improvements such as improved productivity by suppressing spoilage of various coating liquids during production, reduction of equipment burden such as storage equipment, and drastic reduction in product physical property failures, etc. A great effect was obtained.

Claims (1)

[Claims] A method for producing a silver halide photographic material in which a hardening agent having preservative properties is added in-line to a hydrophilic colloid solution, characterized in that the gelatin, which is the hydrophilic colloid, has a calcium content of 1000 ppm or less. A method for producing silver photographic materials.