JPH04333045A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To offer a silver halide photographic material which causes little deterioration of performances for the lapse of time and no carrying failure for an automatic carrying type scanner nor static mark. CONSTITUTION:This silver halide photographic material has at least one silver halide emulsion layer on a transparent supporting body and at least one layer containing a fluorine-base surfactant among layers in the silver halide emulsion layers side. The coating liquid of the photosenstive material is applied, dried and treated by heating at >=30 deg.C.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to a silver halide photographic material having a silver halide photosensitive layer on a transparent support.

0002

BACKGROUND OF THE INVENTION Generally, plastic film supports have strong electrostatic properties, and this often imposes many restrictions on their use. For example, supports such as polyethylene terephthalate are generally used in silver halide photographic materials, but they tend to become electrically charged, especially at low humidity such as in winter. Antistatic measures are especially important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light using automatic printers, as has been the case recently.

When a photosensitive material is charged, static marks appear due to the discharge, or foreign matter such as dust is attached, which causes pinholes to occur, resulting in a significant deterioration in quality. It reduces workability. For this reason, antistatic agents are generally used in photosensitive materials, and recently antistatic agents have been used, such as fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, sulfonic acids, Polymers having phosphoric acid groups in their molecules are used.

In particular, adjustment of the charge series using fluorine-based surfactants or improvement of conductivity using conductive polymers has been widely used. An example is disclosed in which an ionic polymer having a dissociative group is applied.

However, in these conventional techniques, the antistatic ability is significantly degraded by the development process. This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when printing on a processed film, such as with printing photosensitive materials,
Problems such as pinholes may occur due to adhesion of dust. For this reason, for example, JP-A-55-84658 and JP-A-61-17
No. 4542 proposes an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine, or a conductive metal oxide such as tin oxide. These conductive layers are usually provided on the side of the backing layer opposite the emulsion layer and the support. On the other hand, a color scanner is a device that performs both color separation and halftone dot separation of a color original, and prints onto a photosensitive material using laser light. A color scanner is used. Such color scanners generally use a method in which a roll film for printing plates is wound around a rotating drum with the emulsion side facing outward, and the drum is rotated while printing with a laser beam. So-called automatic transport type scanners, in which simply loading photosensitive material in a cassette into the scanner, automatically winds it onto a drum, exposes it, ejects the photosensitive material, or inserts it into an automatic processor are becoming widespread. Became. In this case, the roll film is wound around the drum by rubbing the emulsion surface with a roller and vacuuming the backing layer surface.

However, when the antistatic photosensitive material is passed through this automatic conveyance type scanner, some materials in the conveyance path may induce a large amount of electric charge when they come into contact with the photosensitive material. It has become clear that they stick together electrostatically, causing transportation defects and hindering plate-making operations. Conventionally, matting agents have been used to deal with poor conveyance, but existing matting agents are insufficiently effective, and if used in large quantities to be effective, problems of haze may occur. Furthermore, the application of an antistatic layer sometimes deteriorates the storage stability over time.

[0007]

[Object of the Invention] In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that can be transported without problems even in an automatic transport type scanner and has excellent antistatic ability and storage stability over time. That's true.

[0008]

[Structure of the Invention] The above object of the present invention is to provide
After applying and drying a coating solution of a photosensitive material having at least one silver halide emulsion layer and at least one layer on the side of the silver halide emulsion layer containing a fluorine-based surfactant, the coating solution was dried at 30°C. This is achieved by using a silver halide photographic material obtained by the heat treatment described above.

The present invention will be explained in detail below.

[0010] The temperature of the heat treatment in the present invention is 30°C or higher, preferably 30 to 60°C. More preferably, the temperature is 30 to 50°C. If the temperature is lower than 30°C, curling will not occur, and if the temperature exceeds 60°C, deterioration of photographic performance such as fogging will occur.

[0011] The time required for the heat treatment can be arbitrarily selected from 1 hour to 1 month, but is preferably 6 hours to 14 days.

[0012] The heating treatment may be performed at any time after coating and drying and before exposure, but preferably from immediately after coating and drying in a rolled-up form until cutting into a required size. Another preferred period is after cutting to the required size and before exposure.

[0013] Furthermore, after coating and drying, the film may be rolled up and subjected to heat treatment immediately after drying until it is cut into a required size, and further heat treatment may be performed after cutting and before exposure.

In order to achieve the object of the present invention, it is preferable to carry out the heat treatment with the emulsion layer side facing outward.

A hydrazine derivative or a tetrazolium compound can be added to the photosensitive material of the present invention as a contrast enhancer for use in printing plate making. Further, it is preferable to coat the support with an antistatic layer on the side opposite to the emulsion side. As the hydrazine derivative, it is preferable to use at least one hydrazine derivative represented by the following general formulas [A] and [B] in combination with a nucleation-promoting compound.

[0016]

[Chemical formula 1]

The explanations of each group constituting the above general formulas [A] and [B] are the same as those described on pages 6 to 12 of Japanese Patent Application No. 2-234203, and specific compound examples thereof include (1) to (177) described on pages 12 to 48 of the same patent can also be used in the present invention.

Such hydrazine derivatives are used in combination with nucleation-promoting compounds such as amine compounds, hydrazine compounds, and quaternary onium salt compounds described in Japanese Patent Application No. 2-234203, pages 68 to 144. As for the tetrazolium compound, those represented by the following general formula [T] are preferably used.

[0019]

[Case 2]

The detailed explanation of the general formula [T] is the same as that described on pages 79 to 80 of Japanese Patent Application No. 2-226971, and specific compound examples are given on pages 81 to 85 of the same patent. Examples include T-1 to T-18 listed on page.

[0021] As the fluorine-containing surfactant used in the present invention, the following general formulas [Fa], [Fb], [Fc]
, [Fd] or [Fe].

[0022]

[Chemical formula 3]

[In the formula, R1, R2, R4, R5 and R6
each represents a linear or branched alkyl group having 1 to 32 carbon atoms, such as methyl group, ethyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group , octadecyl group, etc., but it may also be a cyclic alkyl group, and at least one group of R1 and R2 and at least one group of R4, R5, and R6 are substituted with at least one fluorine atom. Further, R1, R2, R4, R5 and R6 each represent an aryl group, such as a phenyl group or a naphthyl group, and these aryl groups represent at least one group among R1, R2 and at least one group among R4, R5, R6. one group is substituted with a group substituted with at least one fluorine atom.

Further, R3 and R7 represent an acid group such as a carboxylate group, a sulfonato group or a phosphoric acid group. ]

002
5]

[C4]

[In the formula, R8 represents an alkyl group having 1 to 32 carbon atoms, such as a methyl group, ethyl group, propyl group, hexyl group, nonyl group, dodecyl group, hexadecyl group, etc. Substituted with at least one fluorine atom. n represents an integer of 1 to 3, n1 is 0 to 4
represents an integer. ]

[0027]

[C5]

[In the formula, R9 represents a saturated or unsaturated linear or branched alkyl group having 1 to 32 carbon atoms. Examples of the saturated alkyl group include methyl group, ethyl group, butyl group, and isobutyl group. , hexyl group, dodecyl group, octadecyl group, etc., and unsaturated alkyl groups include, for example, allyl group, butenyl group, octenyl group, etc. These saturated and unsaturated alkyl groups are substituted with at least one fluorine atom. n2 and n3 represent integers of 1 to 3. Moreover, n4 represents an integer of 0 to 6. ]

[0029]

[C6]

[In the formula, Y is a sulfur atom, a selenium atom, an oxygen atom, a nitrogen atom or a -N(R11)- group (herein, R11
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, such as a methyl group or an ethyl group, and R10 is a group having the same meaning as the group represented by R8 in the above general formula [Fc] or at least one group. Represents an aryl group substituted with a fluorine atom (eg, phenyl group, naphthyl group, etc.). Z represents an atomic group necessary to form a 5- or 6-membered heterocycle, examples of which include a thiazole ring, selenazole ring, oxazole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, Examples include a pyrimidine ring and a triazine ring.

The above heterocycle may further have a substituent such as an alkyl group or an aryl group, and these substituents may be substituted with a fluorine atom.

Next, specific examples of fluorine-containing surfactants represented by the above general formulas [Fa] to [Fe] will be shown, but the compounds that can be used in the present invention are not limited to these. .

When R10 used in the present invention does not contain a fluorine atom, n5 represents an integer of 0 to 2, and n6 represents an integer of 0 to 2.
represents an integer. The amount of the surfactant containing a fluorine atom added to the outermost layer is preferably 1 to 200 mg/m2, more preferably 3 to 100 mg/m2.

(Exemplary compounds)

[0035]

[C7]

[0036]

[Chemical formula 8]

[0037]

[Chemical formula 9]

The fluorine-containing surfactant used in the present invention has a concentration of 0.02 to 800 mg/m2, preferably 0.02 to 800 mg/m2, preferably 0.
．． 05 to 300 mg/m2.

The fluorine-containing surfactant of the present invention is preferably added to the outermost layer of the light-sensitive material.

In the present invention, it is preferable to provide at least one conductive layer on the support. Typical methods for forming the conductive layer include a method using a water-soluble conductive polymer, hydrophobic polymer particles, and a curing agent, and a method using a metal oxide.

Regarding the above-mentioned water-soluble conductive polymer,
Sulfonic acid group, sulfate ester group, quaternary ammonium salt,
Examples include polymers having at least one conductive group selected from tertiary ammonium salts and carboxyl groups. The amount of conductive groups required is 5% by weight or more per polymer molecule. The water-soluble conductive polymer may contain a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group. The number molecular weight of the polymer is 3000
~100000, preferably 3500~5000
It is 0.

Typical examples of water-soluble conductive polymer compounds used in the present invention are listed below, but the invention is not limited thereto.

[0043]

[Chemical formula 10]

[0044]

[Chemical formula 11]

[0045] Still another specific example is Japanese Patent Application No. 2-2
Among the compounds A-1 to A-21 described on pages 35 to 40 of No. 26971, there are compounds other than the above-mentioned representative examples.

The hydrophobic polymer particles contained in the conductive layer of the present invention are composed of so-called latex, which is substantially insoluble in water. This hydrophobic polymer is obtained by polymerizing monomers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. Particularly preferred is 50 mol% or more.

The amide group-containing monomer to be contained in the latex of the present invention is preferably one represented by the following general formula [A].

[0048]

[Chemical formula 12]

[In the formula, R represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. L represents a divalent group, and a represents 0 or 1. R1 and R2 each represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. ] Specific examples of the monomer of the present invention are given below.

[0050]

[Chemical formula 13]

Typical specific examples of the hydrophobic polymer of the present invention are listed below.

[0052] A preferred method for introducing polyalkylene oxide chains into the hydrophobic polymer latex of the present invention is a method by copolymerizing monomers having polyalkylene oxide chains.

As monomers, those represented by the following general formula [M] are preferred.

[0054]

[Chemical formula 14]

Next, typical examples of these monomers will be given.

[0056]

[Chemical formula 15]

[0057]

[Chemical formula 16]

There are two methods for making a hydrophobic polymer into a latex: emulsion polymerization, dissolving a solid polymer in a low boiling point solvent, finely dispersing it, and then distilling off the solvent. Moreover, emulsion polymerization is preferable because a complete product can be produced.

The number molecular weight of the hydrophobic polymer may be 3000 or more, and there is almost no difference in transparency depending on the molecular weight.

Typical examples of the latex of the present invention are listed below.

[0061]

[Chemical formula 17]

[0062]

[Chemical formula 18]

[0063] Still another specific example is Japanese Patent Application No. 2-22
Compounds B-1 to B described in No. 6971, pages 49 to 55
-26 other than the above representative examples.

[0064] As for the epoxy compound of the present invention, it is preferable that the hydroxy group contains an ether condensation group.

Typical specific examples of the epoxy compound of the present invention are listed below.

[0066]

[Chemical formula 19]

[0067]

[C20]

[0068] Still another specific example is Japanese Patent Application No. 2-22
Compounds E-1 to E described in No. 6971, pages 55 to 57
There are cases other than the above-mentioned representative examples among -9.

[0069] The amount of the hydrophobic polymer latex contained in the antistatic layer is preferably 10 mg/m2 to 100 mg/m2.
0mg/m2, particularly preferably 100mg/m2 to 50
0mg/m2, the amount of the water-soluble conductive polymer added is preferably 50mg/m2 to 2000mg/m2, particularly preferably 100mg/m2 to 1000mg/m2, and the amount of the epoxy compound added is preferably 10mg/m2 to 50mg/m2.
00mg/m2, particularly preferably 50mg/m2 to 30
It is 0 mg/m2.

[0070] A dispersant can be used in the antistatic layer, and as such a dispersant, a nonionic activator is used, and a polyalkylene oxide compound is preferably used.

The polyalkylene oxide compound used in the present invention refers to a compound containing at least 2 or more polyalkylene oxide chains and at most 500 or less polyalkylene oxide chains in the molecule, such as polyalkylene oxide and aliphatic alcohols, phenols, fatty acids. , aliphatic mercaptans, organic amines, etc., by condensation reaction with compounds having active hydrogen atoms, or polypropylene glycol,
Polyols such as polyoxytetramethylene polymers, aliphatic mercaptans, organic amines, ethylene oxide,
It can be synthesized by condensing propylene oxide and the like.

The above polyalkylene oxide compound is
There are two polyalkylene oxide chains in the molecule instead of one.
It may also be a block copolymer divided into more than one portion.

At this time, the total polymerization degree of the polyalkylene oxide is preferably 3 or more and 100 or less.

Typical examples of the polyalkylene oxide compounds optionally used in the present invention are shown below.

[Exemplary compounds]

[0076]

[C21]

Next, a method of forming a conductive layer using a metal oxide will be explained.

Crystalline metal oxide particles are preferred as the metal oxide, but those containing oxygen vacancies and those containing a small amount of foreign atoms that form donors for the metal oxide used are generally used. It is particularly preferred because it has high conductivity, and the latter one containing a small amount of a foreign atom that forms a donor for the metal oxide used is particularly preferred because it does not cause fog in the silver halide emulsion.

Examples of metal oxides include ZnO2, Ti
O2, SnO2, Al2O3, In2O3, SiO2,
MgO, BaO, M0O3, V2O5, etc. or composite oxides thereof are preferable, especially ZnO2, TiO2, SnO
2 is preferred.

[0080] As an example containing a different type of atom, for example, SnO2
Addition of Sb etc. to TiO2 or Nb to TiO2
, Ta, etc. are effective. The amount of these different atoms added is preferably in the range of 0.01 to 30 mol%, but 0.1
A range of 10 mol % to 10 mol % is particularly preferred.

[0081] The metal oxide particles used in the present invention are:
It has electrical conductivity, and its volume resistivity is 107Ω.
cm or less, particularly preferably 105 Ωcm or less.

This oxide is described in Japanese Patent Application Laid-Open No. 56-143.
No. 431, No. 56-120519, No. 58-6264
It is stated in No. 7.

[0083] The metal oxide particles are used by being dispersed or dissolved in a binder. The binder that can be used is not particularly limited as long as it has film-forming ability.

In particular, gelatin (lime-treated gelatin, acid-treated gelatin, oxygen-decomposed gelatin, phthalated gelatin, acetylated gelatin, etc.), acetylcellulose, diacetylcellulose, triacetylcellulose, polyvinyl alcohol, polyvinyl acetate, polybutyl acrylate, Polyacrylamide and dextran are preferred.

In order to use the metal oxide more effectively and lower the resistance of the conductive layer, it is preferable that the volume content of the metal oxide in the conductive layer is high. Since at least about 5% of the binder is required to provide this, the volume percentage of the metal oxide is preferably in the range of 5 to 95%.

[0086] The amount of metal oxide used is 0.05 to 10 g/
m2 is preferable, more preferably 0.01 to 5 g/m2
It is. This provides antistatic properties.

In the present invention, the conductive layer may be provided on the photosensitive emulsion side of the transparent support, or may be provided on the opposite side of the transparent support from the photosensitive emulsion side, so-called the back surface. good.

[0088] Such a conductive layer is formed by coating on a transparent support.

[0089] Any transparent support for photography can be used, but polyethylene terephthalate or cellulose triacetate, which is made to transmit 90% or more of visible light, is preferred. More preferred is polyethylene terephthalate from the viewpoint of dimensional stability.

[0090] These transparent supports are prepared by methods well known to those skilled in the art, but in some cases, a slight amount of dye may be added to give them a blue tint so as not to substantially inhibit light transmission. You may do so.

The support may be coated with a subbing layer containing a latex polymer after being subjected to corona discharge treatment. Corona discharge treatment has an energy value of 1mW to 1k.
w/m2min is particularly preferably applied. Particularly preferably, corona discharge treatment is performed again after applying the latex undercoat layer and before applying the conductive layer.

The silver halide emulsion (hereinafter referred to as silver halide emulsion or simply emulsion) used in the present invention includes silver halide such as silver bromide, silver iodobromide, silver iodochloride, and chloride. Any silver halide emulsion commonly used in silver halide emulsions, such as silver chloride and silver chloride, can be used, but monodisperse emulsions are preferred, with a grain size of 3 μm or less, especially 0.5 μm.
1 to 1 μm is preferable.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention.

For example, the silver halide photographic emulsion and backing layer used in the present invention may contain various chemical sensitizers, toners, hardeners, surfactants, thickeners, plasticizers, and slippers, as necessary. Agents, development inhibitors, ultraviolet absorbers, irradiation inhibitors, dyes, heavy metals, matting agents, and the like can be further incorporated by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and backing layer of the present invention.

Supports that can be used in the silver halide photographic material of the present invention include cellulose acetate, cellulose nitrate, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene, polyethylene, baryta paper, and polyolefin-coated supports. paper,
Examples include glass and metal. These supports are subjected to surface treatment if necessary.

After exposure, the silver halide photographic material according to the present invention can be developed by various methods, such as commonly used methods.

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, and aminobenzenes, and other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides. etc. can be included.

[0098]

[Examples] The present invention will be specifically explained below using Examples. It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.

Example 1 8W/(
After corona discharge with an energy of
The coating was applied using a roll-fit coating pan and an air knife at a speed of n.

(Preparation of support having a conductive layer) After corona discharge was applied to polyethylene terephthalate having a thickness of 100 μm which had been subjected to undercoating treatment, an antistatic liquid having the following composition was applied at a rate of 70 m/min to the following amount. Application was done using a quick roll fit coating pan and an air knife.

Water-soluble conductive polymer P-6
0.6g/m2 Hydrophobic polymer particles L-1
0.4g/m2 polyethylene oxide compound
Ao-1 0.06g/m2 Curing agent E
-8
0.2 g/m2 This was dried at 90°C for 2 minutes and heat treated at 140°C for 90 seconds. A support was prepared in which this conductive layer was coated on one side of the support.

(Preparation of Silver Halide Emulsion A) A silver chlorobromide emulsion (62 mol % of silver chloride per mol of silver) was prepared using the simultaneous mixing method. During this mixing, potassium hexabromulodate was added at 5 x 10-8 mol per mol of silver, and potassium hexachloroiridate was added at 8 x 10 mol per mol of silver.
-7 moles were added. Note that the potassium hexabromorodate salt and the potassium hexachloroiridate salt were added after 5% of the final average particle size was formed until the final average particle size was reached. After this, the following sensitizing dye D-1 was added to silver 1
After adding 1.5×10 −4 mol per mol and adsorbing at 50° C. for 40 minutes, exemplified modified gelatin G-8 described in the upper left column of page (4) of JP-A-3-45946 was added. Thereafter, the pH was adjusted to 4.3 with acetic acid, and the mixture was washed with demineralized water, and gelatin was added and dissolved. At that time, the following compounds [A], [B],
A mixture of [C] was added. The obtained emulsion has an average grain size of 0
．． The emulsion consisted of cubic monodisperse particles of 30 μm (coefficient of variation 15%).

(Preparation of emulsion layer coating solution) After adding citric acid and potassium bromide to this emulsion, chloroauric acid and sodium thiosulfate pentahydrate were added and ripened at 60°C to reach maximum sensitivity. The ripening was stopped by adding 50 mg of 1-phenyl-5-mercaptotetrazole and 1 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mole of silver. To this emulsion, 170 mg of the following sensitizing dye D-2 per mole of silver, 4 g of hydroquinone, 2 g of potassium bromide, 10 g of polymer latex P1 having the following structure, 2 g of styrene-maleic acid polymer, and 1N hydroxide. Sodium solution and sodium dodecylbenzenesulfonate as an additive aid and 2,4-dichloro- as a hardening agent.
The sodium salt of 6-hydroxyazine was added.

(Preparation of coating solution for emulsion protective film layer) Add 1-phenyl-4 to an aqueous solution containing 1.1 g of gelatin per 1 m2.
- 5.5 mg of hydroxymethyl-3-pyrazolidone,
25 mg of monodispersed silica with an average particle size of 3 μm, an aqueous solution of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate as a coating aid, citric acid, and the following No. 1
The fluorine-based surfactant shown in the table was added and stirred, and further formalin was added as a hardening agent.

(Preparation of backing layer coating solution) To an aqueous solution containing 2.0 g of gelatin per 1 m2, add 100 mg of water-soluble dye compound III-1 and 40 m of water-soluble dye compound III-2 described below.
g, 80mg of the same III-3, 100m of the same III-4
g, 50 mg of polymer latex P-1, 6 mg of 5-nitroindazole, 60 mg of styrene-maleic acid polymer, 150 mg of colloidal silica, 55 mg of dodecylbenzenesulfone soda, glyoxal, and the above-mentioned exemplified compound E-2 as coating aids. Add and stir.

(Preparation of backing layer protective film layer coating solution) 1
To an aqueous solution containing 1.0 g of gelatin per m2, 12 mg of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate and a dispersion of monodispersed polymethyl methacrylate with an average particle size of 5.5 μm were added. and stir,
Furthermore, glyoxal and sodium salt of 2,4-dichloro-6-hydroxyazine were added as hardening agents.

(Preparation of sample) Using the support having the above antistatic layer, 15W/(m2·mi) was applied to one side of the support.
After corona discharge with the energy of n), the backing layer coating solution and the backing layer protective layer coating solution prepared as above were applied. Also, 15W/(
After corona discharge with an energy of m2·min), an emulsion layer and an emulsion protective film layer were coated. The emulsion layer has a silver content of 4.0
mg/m2, and the amount of gelatin was 1.7 mg/m2, and after drying, it was wound around a core with a diameter of 40 cm so that the emulsion side faced outward.

[0108]

[C22]

[0109]

[C23]

(Heat treatment 1) A photosensitive material wound around a core having a diameter of 40 cm was heat treated at 40° C. for 3 days.

(Heat treatment 2) After the heat treatment 1 described above, cutting was performed. Then, it was wound around a core with a diameter of 7.6 cm with the emulsion layer side facing outward to produce a roll product with a width of 508 mm and a roll of 61 m. This roll product was heat treated at 38°C for 10 days.

(Curling degree test) The curling degree of the obtained sample was measured. A sample of 508 mm x 600 mm was heated to 23°C.
After conditioning the humidity for 2 hours under conditions of 20% RH and placing it on a flat table with the backing layer side up, it was shown by how much the 508 mm side edge lifted. (Evaluation of transportability) 508mm width 61m roll product
, expressed as a percentage of the incidence of conveyance defects when winding and rotation were repeated 100 times using a Chromagraph R3020 recorder manufactured by Hell Graphics.

(Test for Aging) The unexposed sample was divided into two parts, and one part was stored at 23°C and 50% RH for 3 days. After conditioning the remaining sample at 23°C and 50% RH for 8 hours, it was stacked and sealed in a moisture-proof return passage, and heated to 55°C.
The sample was left for 3 days to undergo forced deterioration, and an aging sample was prepared. Both samples were exposed for 10-5 seconds through an optical wedge and a 488 nm interference filter. Thereafter, it was processed under the following conditions using an automatic plate-making machine GR-27 manufactured by Konica Corporation containing the following developer and fixer. The thus obtained samples shown in Table 1 were measured using an optical densitometer Konica PDA65.
The sensitivity and fog density of unexposed areas were measured. The sensitivity was measured for sample No. stored for 3 days under the conditions of 23°C and 50% RH. The relative sensitivity is shown with the sensitivity at a concentration of 1 and 2.5 set as 100.

(Static test) 23 times the unexposed sample
After conditioning the humidity at 20% RH for 2 hours, the sample was rubbed 10 times with a neoprene rubber roller in the dark. Thereafter, development was performed and the occurrence of static marks was examined. Those that occurred are indicated by ×, and those that did not occur are indicated by ○.

<Processing conditions> The processing conditions are as follows.

[Developer formulation] (Composition A) Pure water (ion exchange water)

150ml Ethylenediaminetetraacetic acid disodium salt 2g
diethylene glycol

50g potassium sulfite (55% W/V aqueous solution)

100ml potassium carbonate

50g hydroquinone

15g 5-
Methylbenzotriazole
200ml
1-phenyl-5-mercaptotetrazole
30mg
Potassium hydroxide Amount to adjust the pH of the solution to 10.5 Potassium bromide

4.5g (composition B) Pure water (ion exchange water)

3ml diethylene glycol

50g Ethylenediaminetetraacetic acid disodium salt
25mg acetic acid (90% aqueous solution)

0.3ml 5-nitroindazole
110mg 1-phenyl-3-pyrazolidone
When using a 500 mg developer, the above compositions A and B were dissolved in 500 ml of water in that order to make up to 1 liter.

[Fixer formulation] (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 230 ml
sodium sulfite

9.5g Sodium acetate trihydrate

15.9g boric acid

6.7g Sodium citrate dihydrate
2g acetic acid (
90% W/W aqueous solution)
8.1
ml (composition B)
Pure water (ion exchange water)
17ml sulfuric acid (50% W/W aqueous solution)
5.
8g aluminum sulfate (Al2O3 equivalent content is 8.
1% W/W aqueous solution) When using a 26.5 g fixer, the above compositions A and B were dissolved in 500 ml of water in that order to make up to 1 liter. The pH of this fixer is approximately 4.
．． It was 3.

[Development processing conditions] Process Temperature Time development
34℃ 15 seconds fixation 34℃
Wash with water for 15 seconds, room temperature 1
Drying for 0 seconds 40° C. 10 seconds Each process time also includes the so-called wading conveyance time to the next process.

The results are shown in Table 1.

[0120]

[Table 1]

As is clear from Table 1, the samples of the present invention are excellent in static test and scanner transportability, and also have good storage stability over time.

Example 2 An experiment was carried out in the same manner as in Example 1, except that 30 mg/m2 of the following tetrazolium compound T was added to the emulsion coating solution.

[0123]

[C24]

[0124] As a result, the same results as in Example 1 were obtained.

Example 3 The same evaluation as in Example 1 was carried out in the following manner, except for the conductive support.

(Preparation of Silver Halide Photographic Emulsion B) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using the simultaneous mixing method. During this mixing, 8 x 10-7 mol of K2IrCl6 was added per mol of silver when 90% of the final average particle size was formed. The resulting emulsion contained cubic monodisperse grains with an average grain size of 0.24 μm (coefficient of variation 9%).
). 6 per mole of silver in this emulsion.
．． After adding 5 cc of 1% aqueous potassium iodide solution, modified gelatin was added, and the mixture was washed with water and desalted in the same manner as in Example 1. The pAg at 40°C after desalting was 8.0. Furthermore, the compound used in Example 1 as an antibacterial agent during redispersion [
A mixture of A][B][C] was added.

(Preparation of silver halide photographic light-sensitive material) The silver halide emulsion layer of the following formulation (1) was prepared with a gelatin amount of 2.
．． 0g/m2, silver amount is 3.2g/m2, and on top of that, an emulsion protective layer of the following formulation (2) is applied so that the gelatin amount is 1.0g/m2, In addition, on the other undercoat layer on the opposite side, a backing layer with a gelatin amount of 2.4 g/m2 is applied according to the following recipe (3), and on top of that, a backing layer is coated according to the following recipe (4). A layer was coated so that the amount of gelatin was 1 g/m2, and Sample No. 1 to 18 were obtained.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2
．． 0g/m2 Silver halide emulsion B Silver amount

3.2g/m2 Sensitizing dye: D-3

0.2g/m2 Stabilizer: 4-
Methyl-6-hydroxy-1,3,3a,7-tetrazaindene


30mg/m2 Antifoggant: Adenine

10mg/m2 Surfactant: saponin

0.1g/m2 Hydrazine compound H-1
40mg/m2 Nucleation accelerator N-1
40mg
/m2 S-1

8.0mg/m2 formulation (2) (emulsion protective layer composition) Gelatin

0.9g/m2 Surfactant: S-2

10mg/m2 Surfactant: Shown in Table 2 Matting agent: Average particle size 3.
5μm monodisperse silica
3.0mg/m2 Hardener: 1,3-vinylsulfonyl-2-propanol 4
0mg/m2 prescription (3) (Backing layer composition) III-1

75mg/m2 III-2

30mg/m2
III-3

30mg/m2 gelatin

2.4g/m2
Surfactant: saponin
0.1g/m2
:S-1

6mg/m2 colloidal silica
100mg/m2
Hardener: E-2
55mg/
m2 prescription (4) (backing protective layer composition)
gelatin

1g/m2 Matting agent: Polymethyl methacrylate with an average particle size of 5.0μm


15mg/m2 Surfactant: S
-2
10mg/m2
Fluorine surfactant F-12
5mg/m2
Hardener: Glyoxal
25mg/m2
:H-1

35mg/m2

[0129]

[C25]

[0130]

[C26]

[0131] However, the exposure was performed using an optical wedge and a 633n
was performed in 10 −5 seconds through an interference filter of m. The developer used is the following developer formulation B and fixer formulation using a Konica automatic developing machine GR-26S for quick development processing.
Treated with R. Developer formulation Ethylenediaminetetraacetic acid sodium salt 1g
sodium sulfite
6
0g boric acid

40g hydroquinone
35g
Sodium hydroxide
8g
sodium bromide

3g 5-methylbenzotriazole
0.2g 1-phenyl-5-mercaptotetrazole 0.08g
1-phenyl-4,4-dimethyl-3-pyrazoline 0.2g
add water

Adjust pH with 1l sodium hydroxide

10.5 Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution)
240ml sodium sulfite
1
7g Sodium acetate trihydrate

6.5g boric acid

6.0g Sodium citrate dihydrate
2.0g (composition B) Pure water (ion exchange water)
1
7ml sulfuric acid (50% W/V aqueous solution)

4.7g aluminum sulfate

26.5g (Aqueous solution with AI2O3 equivalent content of 8.1% W/V) 500 g of water when using fixer
The above composition A and composition B were dissolved in this order in 1 ml, and the total volume was made up to 1 liter for use. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
Fixation at 40℃ for 20 seconds
Wash at 35℃ for 20 seconds
Dry at 30℃ for 15 seconds
Table 2 shows the results at 50°C for 15 seconds.

[0133]

[Table 2]

Example 4 (Preparation of support having conductive layer) After corona discharge was applied to a 100 μm thick undercoated polyethylene terephthalate support, a conductive layer having the following structure was coated.

Gelatin

35mg/m2 SnO2/Sb (8/2) (
particle size 0.3μm)
250mg/m2

[0136]

[C27]

[0137] This was dried at 90°C for 2 minutes and heat treated at 140°C for 90 seconds. This conductive layer was coated on only one side of the support and on both sides of the support, respectively.

A sample was prepared in exactly the same manner as in Example 3, with an emulsion layer, an emulsion protective layer, a back layer, and a back protective layer. A test similar to that in Example 1 was conducted using the obtained sample. As a result, it was found that the sample provided with the above-mentioned conductive layer of the present invention produced less static, and better results were obtained than the sample not provided with the conductive layer.

Example 5 Sample No. of Example 1. No. 111 was prepared, and the same evaluation as in Example 1 was performed except that heat treatment A and heat treatment B were performed under the conditions shown in Table 3 below.

(Heat treatment A) After winding around a core having a diameter of 40 cm, heat treatment was performed for 3 days while changing the heating temperature.

(Heat treatment B) After the above heat treatment A, cutting was performed. Then, wrap it around a core with a diameter of 7.6 cm so that the emulsion layer side is on the outside, and make a width of 508 mm and a width of 61 cm.
An m-roll product was made. This roll product was heat treated for 10 days while changing the heat treatment temperature.

The results are shown in Table 3.

[0143]

[Table 3]

[0144]

Effects of the Invention According to the present invention, it was possible to provide a silver halide photographic material which does not cause transport defects in an automatic transport type scanner, does not generate static marks, and exhibits little deterioration in performance over time.

Claims (1)

[Claims] 1. A photosensitive material having at least one silver halide emulsion layer on a transparent support, and at least one layer on the side of the silver halide emulsion layer containing a fluorine surfactant. A silver halide photographic material obtained by applying a coating solution, drying it, and then heat-treating it at 30°C or higher.