JPH04343351A - Silver halide photographic sensitive material and method for packing the same - Google Patents

Abstract

PURPOSE:To provide a sensitive material having excellent antistatic ability, excellent vacuum adhesion at the time of working and excellent dimensional stability. CONSTITUTION:When at least one photosensitive silver halide emulsion layer and at least one antistatic layer are formed on a base to obtain a silver halide photographic sensitive material, after one side of the base is coated and dried and the other side is coated and dried or after both sides of the base are simultaneously coated and dried, the water content of the resulting sensitive material is adjusted at >=30 deg.C temp. and <=16 deg.C dew point for >=1hr and the sensitive material is kept at <=16 deg.C dew point until it is packed.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material and a packaging method for the light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having excellent antistatic properties, vacuum adhesion, and dimensional stability, and a method for packaging the same. Concerning methods of packaging materials.

0002

BACKGROUND OF THE INVENTION Conventionally, plastic films have been widely used as supports for photosensitive materials, but plastic films generally have strong electrostatic properties.

[0003] When a photosensitive material is charged, static marks are generated due to the discharge, or foreign matter such as dust is attached, which causes pinholes, which significantly deteriorates the quality and seriously impairs workability. This causes a decrease in For this reason, antistatic agents are generally used in photosensitive materials. Recently, surfactants, polymer compounds, polymers having sulfonic acid or phosphoric acid groups in the molecule, and the like have been used as antistatic agents.

[0004] In particular, many methods have been adopted to adjust the charge series using fluorine-based surfactants or to improve conductivity using conductive polymers. Examples are disclosed in which ionic polymers having dissociative groups therein are applied.

However, in this method, the antistatic ability is significantly deteriorated due to the development process. Japanese Patent Publication No. 55-84658
No. 61-174542 discloses a technique for a photosensitive material provided with an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine. According to this method, antistatic properties can be maintained even after treatment, but when a hydrophilic colloid layer such as an antihalation layer is provided, cracks occur during storage over time, significantly reducing the commercial value. Furthermore, when an ultra-high contrast emulsion using a tetrazolium compound or a hydrazine compound is applied to a plastic film support having an antistatic layer,
Desensitization occurred during storage over time.

Conventionally, in the printing and plate making industry, there has been a strong demand for photosensitive materials that have excellent storage stability over time in order to streamline inventory management. Photosensitive materials using matting agents on their surfaces exhibit a large decrease in density over time, and it has been desired to develop a means to improve this problem. In recent years, there has also been a demand for shortening the vacuum contact time during exposure, and in particular, it has been desired to provide a photosensitive material that can be exposed without problems even with a vacuum time of 10 seconds or less. For example, the specification of Japanese Patent Application No. 1-228762 discloses the use of a matting agent with a relatively large particle size in order to improve vacuum adhesion, but in this case, the concentration decreases over time and further deteriorates. This was an obstacle to the practical application of vacuum adhesion improvement technology.

On the other hand, dimensional stability of the film is required for printing photosensitive materials used for multi-color printing or the production of precise photographs. Since silver halide photographic materials generally use hydrophilic colloids such as gelatin as a binder, they tend to expand and contract depending on temperature, humidity, etc., which poses a problem. Therefore, U.S. Patent 3,411,91
No. 2 discloses a technique for adding polymer latex into a hydrophilic colloid, and U.S. Pat. No, no. That is, in order to improve dimensional stability, it is necessary not only to take measures on the photosensitive material side, but also total measures such as drying conditions, packaging materials, and packaging methods. Silver halide photographic light-sensitive materials come in the form of rolls or sheets, but in the case of sheet products, the method generally used is to sandwich and enclose the light-sensitive material between cardboard sheets to prevent the light-sensitive material from bending. .

[0008] However, cardboard tends to contain moisture, and its influence cannot be ignored. For example, if cardboard is used without humidity control, the humidity inside the packaging bag will increase. In addition, if the cardboard is completely dried before use to reduce the humidity inside the packaging bag, it tends to absorb the surrounding humidity quickly, so the moisture content of the base paper varies depending on the time required for the process, impairing dimensional stability. It will be done.

[0009]

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned problems, and the first object of the present invention is to prevent deterioration of antistatic ability after development processing, and to reduce desensitization and desensitization during storage over time.
An object of the present invention is to provide a silver halide photographic material that does not cause cracks or the like. A second object of the present invention is to provide a silver halide photographic material that has excellent vacuum adhesion during exposure and suppresses a decrease in density due to storage over time. A third object of the present invention is to provide a method for packaging silver halide photographic materials with excellent dimensional stability.

0010

[Means for Solving the Problems] The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer and at least one antistatic layer on the support. 1 at a temperature of 30℃ or higher and a dew point of 16℃ or lower after coating and drying on one side, after coating and drying on the opposite side, or after coating and drying on both sides simultaneously.
This is achieved by a silver halide photographic light-sensitive material and a method for packaging the light-sensitive material, which are characterized in that the humidity is controlled for a period of time or more, and the dew point is maintained at 16° or less from the end of double-sided coating and drying until the end of the packaging process.

In this case, the outermost layer of the support on the side having the silver halide emulsion layer contains regular silica having an average particle size of 4 μm or more, and the binder moisture content of the portion containing the outermost layer is in terms of weight ratio. It is preferable that the time required for drying from 800% to 200% is 35 seconds or more, and that the coating surface temperature of the outermost layer during that time is 19°C or less, and that the silver halide emulsion layer contains It is preferable that the silver halide emulsion contained contains a tetrazolium compound or a hydrazine compound.

In addition, in a packaging method in which a silver halide photographic light-sensitive material is hermetically sealed in a sealed bag, the humidity is adjusted for 30 minutes or more below the absolute humidity of the packaging work environment, and then the humidity is adjusted for 1 hour under the packaging process conditions.
It is preferable that at least one type of cardboard that has been conditioned for 5 minutes or more is inserted into a sealed bag and hermetically sealed.

The present invention will be explained in more detail below.

When the photosensitive material of the present invention is coated and dried on one side of the support, after each drying process,
In addition, when coating and drying both sides simultaneously, after drying, the humidity is controlled for at least 1 hour at a temperature of 30°C or higher and a dew point of 16° or less, and the dew point is 16° or less from the time both sides are coated and dried until the end of the packaging process. is maintained. The term "humidity control for 1 hour or more after completion of drying" will be described later.

The method for coating and drying the silver halide photographic material of the present invention will be explained below. Generally, photosensitive materials are formed by coating a support with a coating solution containing a hydrophilic colloid such as gelatin as a binder. Generally, after coating, the coating is cooled and solidified in low-temperature air with a dry bulb temperature of -10 to 15 DEG C., then the temperature is raised to evaporate and remove moisture, and when drying is completed, it is brought into contact with air at room temperature.

[0016] The moisture content of gelatin immediately after coating is 20
The moisture content of gelatin is around 800%.
It has been found that the drying time required from % to 200% and the coating surface temperature during that time affect concentration loss over time.

In the present invention, the gelatin moisture content is 80
The time required for drying from 0% to 200% is preferably 35 seconds or more, and particularly preferably 40 seconds or more. Also, the coating surface temperature during that time was 19℃.
The temperature is preferably below, particularly preferably 17°C or below. The moisture content of gelatin here is the weight ratio of water and gelatin, and the coating surface temperature is a value expressed by the wet bulb temperature of drying air.

[0018] In the present invention, in the step of applying the coating layer, cooling it, and then drying it, from the time when the average surface temperature of the coating layer rises to a temperature 1°C lower than the temperature of the air with which it is in contact,
Contact with air at 35°C to 80°C for 5 seconds or more within minutes. Here, the average surface temperature of the coating layer is 1°C higher than the air in contact with it.
The point at which the temperature rises to a low temperature usually corresponds to a range in which the moisture content in the gelatin composition is in the range of 60 to 20%, and the end of drying in the present invention is defined as this point. Dew point 1
Humidity control at 6℃ or below means that from this point on, the humidity will be 80℃ or above 35℃.
The light-sensitive material is brought into contact with air at a temperature of .degree. Contacting the photosensitive material with air at a temperature of 35° C. or higher and 80° C. or lower approximately corresponds to contacting the photosensitive material with air having a relative humidity of 25 to 1%. This humidity adjustment is preferably carried out within 5 minutes after completion of drying.

The packaging method of the present invention will be explained in detail below. Although it is generally desirable for the working environment conditions in the packaging process to be low humidity, the conditions must be determined in consideration of the effects of electrostatic charges, etc.

[0020] The packaging process in the present invention is carried out at a dew point (DP) of 16°C or lower.

[0021] In the present invention, when sealing and sealing, at least one type of cardboard that has been conditioned for 30 minutes or more below the absolute humidity of the packaging work environment, and then sealed for at least 15 minutes under the packaging process conditions. It is preferable to insert it inside. The difference in absolute humidity between the packaging process and inside the packaging bag is preferably within 0.35%,
More preferably, it is within 0.3%.

The cardboard used in the present invention is not particularly limited as long as it is commonly used as a packaging material for silver halide photographic materials, and the cardboard may be stacked for humidity control.

In the present invention, the outermost layer of the support on the side containing the silver halide emulsion layer contains 4 mg/m2 or more of a regular and/or amorphous matting agent with a particle size of 4 μm or more, and It is preferable that the surface smoother value is 25 mmHg or more, and furthermore, it is desirable to also contain a regular and/or irregularly shaped matting agent with a particle size of less than 4 μm. In this case, at least one of the matting agents is
It is particularly preferable to contain up to 80 mg/m2. Furthermore, it is particularly preferable to contain at least one kind of regular and/or amorphous matting agent having a particle size of less than 4 μm in an amount of 4 mg/m 2 to 80 mg/m 2 .

[0024] Also, the fact that the matting agent is contained in the outermost layer means that
It is sufficient that at least a part of the matting agent is contained in the outermost layer, and a part of the matting agent may reach layers below the outermost layer.

[0025] Also, in order to fulfill the basic function of a matting agent,
It is desirable that a portion of the matting agent be exposed on the surface. Further, the matting agent exposed on the surface may be part or all of the added matting agent. How to add the matting agent:
The matting agent may be dispersed in a coating liquid in advance and applied, or a matting agent may be sprayed after the coating liquid is applied and before drying is completed. Furthermore, when adding a plurality of different matting agents, both methods may be used in combination.

As the matting agent used in the present invention, any known matting agent can be used. For example, silica as described in Swiss Patent No. 330,158, glass powder as described in French Patent No. 1,296,995, British Patent No. 1,
173,181; inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; US Pat.
, 322,037, Belgian Patent No. 625
, 451 or British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158,
Organic particles such as polyacrylonitrile as described in US Pat. No. 3,079,257 and polycarbonate as described in US Pat. No. 3,022,169 can be included.

The above matting agents may be used alone or in combination. As a regular matting agent, the shape of the matting agent is preferably spherical, but other shapes such as a flat plate shape or a cubic shape may also be used. The size of the matting agent is expressed by the diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle size of the matting agent refers to the value of the diameter converted into a sphere.

The silver halide photographic material of the present invention has at least one antistatic layer. By providing an antistatic layer, it is possible to suppress the generation of static marks that cause quality deterioration, and to reduce the humidity during packaging work and inside the packaging bag. As the antistatic layer, Japanese Patent Publication No. 46-24159, Japanese Patent Application Laid-Open No. 48-89979, U.S. Pat. No. 2,882,157, U.S. Pat. No. 2,972,535,
JP-A-48-20785, JP-A-48-43130, JP-A-48-90391, JP-A-46-24159, JP-A-4
No. 6-39312, No. 48-43809, Japanese Unexamined Patent Publication No. 1973
The compound described in JP-A-49-9116 is further used as a fluorosurfactant for adjusting the charge series or as a conductive polymer for improving conductivity.
An ionic polymer having a dissociative group in the polymer main chain as disclosed in No. 5, No. 49-121523 can be used. In addition, regarding the deterioration of antistatic ability due to development processing and other factors,
In No. 542, an antistatic layer consisting of a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine can be employed. According to this method, it is said that there is less deterioration of antistatic ability during development processing and other processes. As seen in Japanese Patent Application No. 63-330863 and others, combinations of various water-soluble conductive polymers, hydrophobic polymers, and curing agents have been proposed, and these can be effectively utilized.

Particularly in the present invention, it is preferable to provide an antistatic layer containing at least a water-soluble conductive polymer, a hydrophobic polymer, and a curing agent. Although it is possible to form a transparent layer by using a water-soluble conductive polymer alone, it is undesirable because it is easily affected by drying conditions, such as causing cracks when dried. Therefore, in the present invention, a method that also contains hydrophobic polymer particles is preferred.

The water-soluble conductive polymer used in the present invention has at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. Examples include polymers containing monomers having In the present invention, a homopolymer consisting only of these monomers or a copolymer with other monomers may be used. In the present invention, among these conductive groups, sulfonic acid groups, sulfuric acid ester groups, and quaternary ammonium bases are preferred. It is necessary that the conductive group is contained in an amount of 5% by weight or more per polymer molecule. In addition to the above-mentioned monomers having conductive groups, the water-soluble conductive polymer used in the present invention includes carboxyl groups, hydroxyl groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, vinyl It may also contain a monomer having a sulfonic acid group. In this case, monomers having a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group, or an aldehyde group are preferred. It is necessary that these groups be contained in an amount of 5% by weight or more per polymer molecule. The molecular weight of the polymer is 300
0 to 100,000 is preferable, more preferably 3,500
~50,000.

Examples of water-soluble conductive polymers used in the present invention are listed below, but the present invention is not limited thereto.

[0032]

[Formula 1] In the above A-(1) to (3), x and y each represent mol% of the monomer component, and Mn represents the average molecular weight (in this specification, average molecular weight means number average molecular weight). ).

[0033] In the present invention, furthermore, Japanese Patent Application No. 2-982
Compounds shown in No. 28, pages 18 to 30 (excluding A-3 and A-9 in the cited document) can also be used. These polymers can be obtained by polymerizing monomers that are commercially available or obtained by conventional methods. The amount of these compounds added is preferably 0.01 g to 10 g/m2, particularly preferably 0.1 g to 5 g/m2.

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer used in the present invention are contained in the form of a so-called latex which is substantially insoluble in water.

[0035] The type of hydrophobic polymer used in the present invention, the addition method, etc. are described in Japanese Patent Application No. 155695/1995, page 38, page 8.
It is as shown from line 7 to page 39, line 7.

As the surfactant used during emulsion polymerization, it is preferable to use an anionic surfactant or a nonionic surfactant, and the amount used is preferably 10% by weight or less based on the monomer. Use of a large amount of surfactant is not preferred because it causes clouding of the conductive layer. The hydrophobic polymer may have a molecular weight of 3000 or more, and there is almost no difference in transparency depending on the molecular weight. Specific examples of the above-mentioned hydrophobic polymer include Japanese Patent Application No. 3, No. 2-155695.
The same compounds as shown on page 9, line 11 to line 45 and the following exemplified compounds are mentioned.

[0037]

[Case 2]

[0038] The curing agent that can be used in the antistatic layer in the present invention is preferably an epoxy type curing agent. The same compounds as shown in the 6th line and the following compounds may be mentioned.

[0039]

embedded image The above compound is commercially available and can be easily obtained. The addition method may be by dissolving it in water or an organic solvent such as alcohol or acetone and adding it as is, or by dispersing it using a surfactant such as dodecylbenzenesulfonate or nonylphenoxyalkylene oxide and then adding it. You can. The preferred addition amount is 1 to 1000 mg/m
It is 2.

Further, in the present invention, the effect can be further enhanced by using triphenylphosphine represented by the following general formula [D] together with the above-mentioned curing agent.

[0041]

embedded image [In the formula, R1 to R3 each independently represent a substituted or unsubstituted alkyl group, hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, alkoxy group, etc. ]

004
2] In the present invention, triphenylphosphine is not particularly limited, but as specific examples, the compounds shown below are preferably used.

[0043]

[C5]

The present invention is effective when applied to printing photosensitive materials, particularly to return films, and for this reason, tetrazolium compounds such as those disclosed in JP-A-62-11253 and JP-A-62-210458 can be used as contrast enhancing agents. Hydrazine compounds as disclosed in 62-21045
A polyalkylene oxide compound such as that disclosed in No. 8 may be contained within a range that does not impair photographic performance.

In the present invention, it is preferable to add a tetrazolium compound or a hydrazine compound to the silver halide emulsion. In the present invention, the contrast enhancer may be added to a layer adjacent to the emulsion layer.

The hydrazine compound preferably used in the present invention is represented by the following general formula [H].

[0047]

[Image Omitted] General formula [H] In the formula, A represents an aryl group or a heterocyclic imino methylene group containing at least one sulfur atom or oxygen atom, n represents an integer of 1 or 2,
A1 and A2 both represent a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, R is a hydrogen atom,
It represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, an oxycarbonyl group, or an -O-R3 group, and R3 represents an alkyl group or a saturated heterocyclic group.

In the present invention, compounds represented by the following general formula [A] or [B] are further preferred.

[0049]

embedded image In the formula, A, R1, R2 and R3 are as described in Japanese Patent Application No. 2-234203, page 6, line 1 to page 12, line 4, respectively.

Representative compounds represented by the above general formula [A] or [B] include those shown below. However, it goes without saying that the specific compounds of general formulas [A] and [B] that can be used in the present invention are not limited to these compounds.

[0051]

[Chemical formula 8]

[0052]

[Chemical formula 9]

[0053]

[Chemical formula 10] Still another specific example is Japanese Patent Application No. 2-234203 No. 1
Compounds (1) to (17) described on pages 2 to 48
There are cases other than the above-mentioned representative examples in 7).

The compound according to the present invention is disclosed in Japanese Patent Application No. 2-2342.
It can be synthesized by the method shown in No. 03, pages 49 to 67.

The amount of the hydrazine compound represented by the general formula [H] added is preferably 10-5 to 10-1 mol/silver 1 mol, more preferably 10-4 to 10-2 mol/silver 1 mol.
It is a mole.

Next, the tetrazolium compound used in the present invention will be explained.

The tetrazolium compound can be represented by the following general formula.

[0058]

embedded image In the present invention, R1 represented by the above general formula [T],
When R2 and R3 are phenyl groups, the substituents for R1, R2, and R3 are preferably hydrogen atoms or those having a negative or positive Hammett's sigma value (σP), which indicates the degree of electron attraction. Particularly preferred are groups having a negative sigma value.

A more detailed explanation of the compound represented by the above general formula [T] is as described in JP-A-2-115831, page 194, lower left, lines 1 to 18. Specific examples of the compound represented by the general formula [T] used in the present invention are listed below, but the present invention is not limited thereto.

[0060]

[Chemical formula 12] In addition to the above compounds, JP-A-2-115831 No. 194
The exemplified compounds shown on pages 1 to 195 (excluding I-2) can also be mentioned as specific examples.

The above tetrazolium compound is the silver halide 1 contained in the silver halide photographic light-sensitive material of the present invention.
From about 1 mg to 10 g per mole, preferably about 10 m
Preferably, the amount is in the range from 1.5 g to about 2 g.

In the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide used in ordinary silver halide emulsions can be used, and preferably negative-working silver halide is used. It is silver chlorobromide containing 50 mol% or more of silver chloride as an emulsion. The silver halide emulsion used in the present invention may have a single composition, or may contain grains of a plurality of different compositions in a single layer or in a plurality of layers.

Regarding the shape, grain size, mixing method, and chemical sensitization method of the silver halide grains used in the present invention,
This is as described in JP-A-2-115831, page 199, top right line 3 to page 200, top right line 11. However, as a method for removing unnecessary soluble salts after the growth of silver halide grains is completed, see Research Disclosure 17.
It can be carried out based on the method described in No. 643.

In practicing the present invention, various stabilizers,
Silver halide solvents, crystal habit control agents, etc. may also be used.

The photosensitive material of the present invention preferably contains a polymer latex, and examples of the polymer latex that can be contained in the photosensitive material include US Pat. 28
No. 6, No. 3,411,911, No. 3,311,912
No. 3,525,620, Research Disclosure magazine,
No. 195 19551 (July 1980) and the like, hydrates of vinyl polymerization such as acrylic esters, methacrylic esters, and styrene are preferred.

The average particle diameter of the polymer latex used in the present invention is preferably in the range of 0.05 to 1 μm, particularly preferably 0.2 to 0.1 μm.

In the present invention, the polymer latex may be contained on only one side of the support or on both sides, but it is preferably contained on both sides. When the polymer latex is contained on both sides of the support, the type and/or amount of polymer latex contained on each side may be the same or different.

[0068]Although the layer to which the polymer latex is added is optional, for example, when it is added to the side of the support that contains the silver halide photosensitive layer, it may be added to the silver halide photosensitive layer. It may also be included in the top non-photosensitive colloid layer, commonly referred to as the protective layer. For example, when an intermediate layer exists between the silver halide photosensitive layer and the uppermost layer, it may be contained in the intermediate layer. Furthermore, the polymer latex may be contained in a single layer or in a plurality of layers (not limited to two layers) formed in any combination.

Depending on the purpose, the light-sensitive material of the present invention may further contain various additives known in the photographic material industry, such as sensitizing dyes, dyes for preventing halation and absorbing ultraviolet light, and stabilizing agents for preventing fogging and preventing deterioration of sensitivity. Agents, thickeners, plasticizers, surfactants, matting agents, slipping agents, optical brighteners, etc. can be used. For example, these additives are more specifically:
Research Disclosure Volume 176 Item 17
643 (December 1978) and Volume 187 Item
18716 (November 1979), and the relevant parts are summarized in the table below.

Additive type RD17
643 RD187161.
Chemical sensitizer page 23
Page 648, right column 2. Sensitivity enhancer
Same as above 3. spectral sensitizer
pages 23-24
Page 648 right column ~ Super sensitizer

Page 649, right column 4. brightener
24 pages 5. Antifoggant
pages 24-25
Page 649 right column and stabilizer 6. Light absorbers, filters pages 25-26
Page 649 right column ~ Dyes, ultraviolet absorbers
Page 650 left column 7. anti-stain agent
Page 25 right column
Page 650 left column to right column 8. dye image stabilizer
25 pages 9. Hardener
26 pages 65
Page 1 left column 10. binder
Page 26 Same as above 11. Plasticizer/Lubricant page 27
Page 650, right column 12. Coating aids/surfactants pages 26-27
Same as above 13. Static inhibitor
27 pages
Same as above

For the support and undercoat layer used in the photosensitive material of the present invention, those known in the industry can be used.

[0072]

[Examples] Specific examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 A negative-type silver halide photosensitive material was prepared as a photosensitive material for bright room printing in the following manner.

(Preparation of emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol % was prepared as follows.

An aqueous solution containing 23.9 mg of pentabromorodium potassium salt, sodium chloride, and potassium bromide per 60 g of silver nitrate and an aqueous silver nitrate solution were simultaneously mixed in an aqueous gelatin solution at 40° C. for 25 minutes to form average grains. Silver chlorobromide emulsions each having a diameter of 0.20 μm were prepared.

This emulsion contains 6-methyl-4- as a stabilizer.
Hydroxy-1,3,3a,7-tetrazaindene 2
After adding 00 mg, the mixture was washed with water and desalted.

After adding 20 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene, sulfur sensitization was carried out. After sulfur sensitization, the required amount of gelatin was added, 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added as a stabilizer, and a finished emulsion was prepared to 260 ml with water. .

(Preparation of latex (L) for emulsion addition) Add 0.25 kg of KMDS (dextran sulfate ester sodium salt) manufactured by Meito Sangyo and 0.05 kg of ammonium persulfate to 40 liters of water and stir at a liquid temperature of 81°C. 4.51 kg of n-butyl acrylate under nitrogen atmosphere
, a mixture of 5.49 kg of styrene and 0.1 kg of acrylic acid was added over 1 hour, then 0.005 kg of ammonium persulfate was added, and the mixture was further stirred for 1.5 hours, cooled, and adjusted to pH 6 with aqueous ammonia. Adjusted to.

The obtained latex liquid was filtered using a Whoman GF/D filter and made up to 50.5 kg with water to obtain a monodisperse latex (with an average particle size of 0.25 μm).
L) was created.

[0080] The emulsion and latex for emulsion addition (L)
A coating solution for a silver halide emulsion layer was prepared as follows by adding the following additives to the solution.

(Preparation of coating solution for emulsion layer) After adding 9 mg of compound (A) as a bactericide to the emulsion solution, the pH was adjusted to 6.5 using 0.5N sodium hydroxide solution, and then a tetrazolium compound was added. Add 360 mg of (T-2), and further add 5% saponin aqueous solution per 1 mole of silver halide.
ml, sodium dodecylbenzenesulfonate 18
0 mg, 80 mg of 5-methylbenztriazole, 43 ml of the emulsion addition latex (L), 60 mg of the following compound (M), and 280 mg of a styrene-maleic acid copolymer aqueous polymer as a thickener were sequentially added. A coating solution for an emulsion layer was prepared by adding water to make up 475 ml.

Next, an emulsion protective film coating solution was prepared as follows.

(Preparation of coating solution for emulsion protective film) Gelatin 3
Add pure water to 5.2 g, swell and dissolve at 40°C, then add 1% aqueous solution 2 of the following compound (Z) as a coating aid.
5cc, the following compound (N) 5. as a filter dye.
3 g and 4.4 g of the following compound (D) were added one after another, and the pH was adjusted to 6.0 with citric acid solution to bring the total volume to 1 liter. Amorphous silica shown in Table 1 was added as a matting agent to this solution to prepare emulsion protective film coating solutions P-1 to P-3.

[0084]

[Table 1]

[0085]

[Chemical formula 13]

[0086]

[Chemical formula 14]

Next, a backing layer coating solution used for coating the lower backing layer was prepared as follows.

(Preparation of coating solution B-1 for backing layer) After swelling 36 g of gelatin in water and dissolving it by heating, 1.6 g of the following compounds (C-1) and (C-2) were added as dyes. 31
0mg, 1.9g of (C-3), 2g of the above compound (N)
．． Add 9 g as an aqueous solution, then add 11 ml of a 20% aqueous solution of saponin, and add the following compound (C-4) as a physical property modifier.
Add 5g of and further add the following compound (
63 mg of C-5) was added. To this liquid, 800 g of a water-soluble styrene-maleic acid copolymer was added as a thickener to adjust the viscosity, and the pH was adjusted to 5.4 using an aqueous citric acid solution. ) to 2.0
g, and finished up to 960 ml with water to prepare backing layer coating liquid B-1.

[0089]

[Chemical formula 15]

[0090]

[Chemical formula 16]

Next, backing layer protective film coating liquid B-2 was prepared as a protective film for the backing layer in the following manner.

(Preparation of backing layer protective film coating solution B-2) Swell 50 g of gelatin in water, dissolve it by heating, add 340 mg of 2-sulfonate-succinic acid bis(2-ethylhexyl) ester sodium salt, and add sodium chloride. 3
．． In addition, 1.1 g of glyoxal and 540 mg of mucochloric acid were added. Add to this 40 mg of spherical polymethyl methacrylate with an average particle size of 4 μm as a matting agent.
/m2, and the total volume was made up to 1000 ml with water to prepare protective film coating liquid B-2.

[Preparation of support having an antistatic layer] After corona discharge was applied to a subbed-treated polyethylene terephthalate film with a thickness of 100 μm at an energy of 50 W/m2·min, a coating solution for an antistatic layer having the following composition was applied. Coating was carried out using a roll-fit coating pan and an air knife at a speed of 30 m/min to the following amounts.

Water-soluble conductive polymer (A)
0.6 g/m2 hydrophobic polymer particles (B)
0.3 g/m2 Hardener (H)
0
．． 15g/m2 Nonionic surfactant (C)
After coating at 0.06 g/m2, it was dried at 90°C for 2 minutes and then heat treated at 140°C for 90 seconds to prepare a support having an antistatic layer.

[0095]

[Chemical formula 17]

[Preparation of evaluation sample] Coating solution B-1 for backing layer and coating solution B-2 for backing layer protective film were simultaneously coated on the side of the support having the antistatic layer and dried under the following conditions. The humidity was adjusted as shown in Table 3.

Next, coat the emulsion layer coating solution and the emulsion protective film coating solution (P-1, P-2) on the opposite side of each support.
Or P-3) after simultaneous multilayer coating and drying under the following conditions Table 3
The humidity was adjusted as shown in .

<Drying conditions during coating> After coating the coating solution at 35°C, it was treated with cold air at 5°C for 6 seconds to cool and solidify, and then drying air at a dry bulb temperature of 23°C and relative humidity of 20% was applied. , coating surface temperature 16°C, coating layer gelatin moisture content 150
It was dried to a moisture content of 0%, and then dried to a moisture content of 900% using drying air at a drying temperature of 27° C. and a relative humidity of 20%. Further, as shown in Table 3, the gelatin was dried according to the following drying condition A using drying air at a drying temperature of 34°C from 800% to 200%. Average temperature of coated surface is 33℃
After 5 seconds from the time when the drying condition B was reached, drying was carried out according to the following drying condition B.

After drying, the humidity was adjusted as shown in Table 3. Next, each sample was cut under the dew point environment shown in Table 3, sealed in a bag that does not allow any outside air to pass through, and designated as sample No.
．． 1 to 16 were created.

[0100]

[Table 2] The development processing applied to the evaluation sample was carried out according to the processing conditions shown below using a developing processing solution having the formulation shown below.

[Developer formulation] (Composition A) Pure water (ion exchange water)
1
50ml Ethylenediaminetetraacetic acid disodium salt
2g
diethylene glycol

50 g potassium sulfite (55% w/v aqueous solution)

100ml potassium carbonate

50 g hydroquinone

15 g 5-methylbenzotriazole
200ml 1-phenyl-5-mercaptotetrazole
30mg potassium hydroxide

Amount to adjust the pH of the solution to 10.9 Potassium bromide
4.5 g
(Composition B) Pure water (ion exchange water)

3ml diethylene glycol

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

0.3ml 5-nitroindazole

110mg 1-phenyl-3-pyrazolidone
500ml of water when using 500mg developer
The above composition A and composition B were dissolved in this order in 1 liter, and the final volume was made up to 1 liter, which was then used.

[Fixer formulation] (Composition A-1) Ammonium thiosulfate (72.5% w/v aqueous solution) 230 ml
sodium sulfite
9
．． 5 g Sodium acetate trihydrate

15.9 g boric acid

6.7 g Sodium citrate dihydrate
2 g acetic acid (
90% w/w aqueous solution)
8.1m
l (Composition B-1) Pure water (ion exchange water)

17ml sulfuric acid (50% w/w aqueous solution)

5.8 g aluminum sulfate (Al2O3
aqueous solution with a converted content of 8.1% w/w) 26.5 g
When using the fixer, the above composition A-1 and composition B-1 were dissolved in 500 ml of water in that order to make up to 1 liter. The pH of this fixer was about 4.3.

[Development processing conditions] (Process) (Temperature) (Time) (Tank capacity) Development 34°C
15 seconds 20 liter fixation
34℃ 15 seconds Wash with 20 liters of water Room temperature 10 seconds
15 liters dry 40℃
Each process time of 10 seconds also includes the so-called wading conveyance time to the next process.

Evaluation method <Temporary storage surrogate test> 1 for each packaged sample
One film was stored frozen at -26°C, and the other film was stored in a thermostat at 40°C for 3 days, each film was developed, and the humidity was conditioned at 23°C and relative humidity of 55% for 1 day. rear,
Surface resistivity was measured under the same environment.

<Peel charging property test> The treated film was
After conditioning the sample at a temperature of 20% relative humidity for one day, the sample was brought into contact with neoprene rubber in the same environment and peeled off 10 times, and immediately thereafter the amount of charge was measured. The above results are shown in Table 3.

[0106]

[Table 3]

Example 2 Tetrazolium compound (T) added to the emulsion layer of Example 1
) The following hydrazine compound (H-1) was used as a contrast enhancing agent. As a result, the same results as in Example 1 could be obtained. Incidentally, a developer having the composition B shown below was used, and the development conditions were 38° C. for 20 seconds.

[0108]

[Chemical formula 18]

[Developer B] Hydroquinone

45.0 g N-methyl p-aminophenol 1/2 sulfate
0.8 g sodium hydroxide

15.0 g potassium hydroxide

55.0 g 5.Sulfosalicylic acid
45.0 g
Boric acid

35.0 g potassium sulfite

110.0 g Ethylenediaminetetraacetic acid disodium salt
1.0 g potassium bromide
6.0
g 5-methylbenzotriazole
0.6
g n-butyl diethanolamine
15.0
g Add water

1 liter

(pH=11.6)

0110
Example 3 A negative film for darkroom photography was prepared as follows.

In Example 1, the amount of pentabromorodium potassium salt used in emulsion preparation was 25 μg per 60 g of silver nitrate, the silver bromide content was silver chlorobromide with a silver bromide content of 25 mol %, and the following sensitizing dye ( C) was added to prepare an emulsion. Using this emulsion, samples were prepared and evaluated in the same manner as in Example 1. As a result, the same results as in Example 1 could be obtained.

[0112]

[Chemical formula 19]

Example 4 A high-sensitivity negative film for bright room use was prepared as follows. (Preparation of sample) In an acidic atmosphere with nitric acid at pH 3.0, while maintaining the silver potential (EAg) at 170 mV,
[Solution B] was added into [Solution B] and mixed by controlled double jet method with EAg controlled with 1N NaCl, and [Solution C] was added at the same reaction temperature as [Solution B] until the addition time was 2 minutes. Add at the addition flow rate, and then add E of [solution B]
0.99 of the addition flow rate while controlling Ag with 1N NaCl.
A silver halide emulsion was prepared by adding at twice the flow rate. The average grain size of the obtained silver halide grains was 0.08 μm.

[Solution A] Gelatin

5.6 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% ethanol solution
0.56ml sodium chloride

0.12 g concentrated nitric acid

0.4
3ml distilled water

445ml [Solution B] Silver nitrate

60 g concentrated nitric acid

0.208ml
Distilled water

85.2ml [Solution C] Gelatin

3 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% ethanol solution
0.3ml potassium bromide

4.2 g sodium chloride
18.6 g
Na3RhCl61% aqueous solution
0.
02ml distilled water

87.3ml [Solution D] Gelatin

1.4 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% methanol solution
0.14ml distilled water

Each silver halide grain had a silver chloride content of 90 mol %, a rhodium content of 2 x 10 -6 mol per mol of silver halide, and a monodispersity of 8 to 15%.

[0115] A metallic silver electrode and a double junction type saturated Ag/AgCl comparison electrode were used to measure the EAg value. (The electrode configuration used was a double junction disclosed in Japanese Patent Application Laid-open No. 57-197534.)

[0116] Furthermore, for the addition of [Solution B] and [Solution C],
A variable flow rate roller tube metering pump was used.

During the addition, the emulsion was sampled to confirm that no new grains were generated using an electron microscope, and it was confirmed that the amount added did not exceed the critical growth rate in the system.

To each of the emulsions thus prepared, 200 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added per mole of silver halide, and the pH was adjusted to 5.7 with sodium carbonate. and then [Solution D] was added. Thereafter, each silver halide emulsion was washed with water and desalted in a conventional manner, and then
8 mg of 6-methyl-4-hydroxy-1,3,3a,
After adding 7-tetrazaindene and 150 mg of potassium bromide, sulfur sensitization was performed. 6 as a stabilizer after sulfur sensitization
570 mg of -methyl-4-hydroxy-1,3,3a,7-tetrazaindene per mole of silver halide and 25 g of gelatin were added. Further, the following additives were added to prepare an emulsion layer coating solution, and the same emulsion protective film coating solution, backing layer coating solution, backing layer protective film coating solution, and support as in Example 1 were used. Samples were prepared in the same manner. Then, when the same treatment as in Example 1 was carried out, completely the same results as in Example 1 were obtained.

[Coating liquid additive for emulsion layer] Saponin

100mg/m2 potassium bromide

3mg/m2
Desensitizing dye (DS-1)

1mg/m2 Sodium hydroxide

10mg/m2 Said tetrazolium compound (T-2)
45mg/m2 Sodium dodecylbenzenesulfonate
21mg/m2 Butyl acrylate
Styrene-acrylic acid copolymer latex 1
g/m2 5-methylbenzotriazole

10mg/m2 5-phenyl-1-mercaptotetrazole 11.5m
g/m2 2-Mercaptobenzimidazole-5-
Sulfonic acid 1mg/m2 Benzyl-triphenylphosphonium chloride
5mg/m2 Said compound (M)

5.8mg/m2

0
120]

[C20]

Example 5 In the sample preparation of Example 4, except for the desensitizing dye (DS-1) and the tetrazolium compound (T) in the emulsion layer coating solution,
Hydrazine compound (H-1) used in Example 2 instead
A sample was prepared in the same manner as in Example 4, except that 10 mg/m2 of the following compound (O) was added to the emulsion protective film coating solution.

[0122]

[C21]

(Evaluation) A sample was prepared in the same manner as in Example 4, except that a developer with composition B was used and the processing conditions were 38° C. and 20 seconds, and the same evaluation was performed. . As a result, the same results as in Example 4 could be obtained.

Example 6 The photosensitive material sample prepared in Example 1 (photosensitive material of sample No. 5) was cut in an environment of a temperature of 23°C and a relative humidity of 35% (dew point of 6°C), and the permeation of outside air was measured. An evaluation sample was prepared by sealing the sample with no wrapping paper.

[0125] At that time, cardboard prepared under the conditions shown in Table 4 was simultaneously enclosed in the package, and samples S1 to S shown in Table 5 were placed inside the package.
10 (packaged immediately after the first and second humidity conditioning) was obtained. In addition, the cardboard processed under the conditions of Table 4 above at 23°C and 35% relative humidity was left for 2 hours (approximately equivalent to the actual packaging work time) and then packaged. Samples T1 to T10
I got it.

[0126]

[Table 4] The samples thus obtained were opened in an environment with an environmental temperature of 23° C. and an environmental relative humidity of 40%, and after being conditioned for 2 hours, the following dimensional stability tests were conducted.

(Dimensional stability test) The sample, which had been conditioned as described above, was heated to 560 mm at an environmental temperature of 23°C and a relative humidity of 40%.
I made scratches at the intervals. This sample was automatically developed using the following developer and fixer under the following development conditions.

[0128] Next, the treated sample was rehumidified for 2 hours in an environment with an ambient temperature of 23°C and a relative humidity of 40%, and then the actual length of the scratches on the sample was measured. The value obtained by subtracting this actual length from 560 mm was expressed as the dimensional stability in μm. A positive value indicates elongation due to automatic development processing, and a larger value indicates poorer dimensional stability.

[0129] The absolute humidity inside the packaging bag of the sample, which was processed and packaged using cardboard as described above, was measured. In addition, the dimensional stability of the samples packaged immediately and 2 hours after the cardboard humidity conditioning was examined. The results are shown in Table 5.

Development processing conditions Step Temperature (°C) Time (seconds) Tank capacity (liters) Development 2
8 30
20 Fixation 28
20
20 Washing with water 18
20 15
Drying 40 2
5 20 Dry heat transfer coefficient: 95 kcal/hr·m2·°C Automatic processor installation environment temperature and humidity: 23°C, relative humidity 40% Each process also includes the so-called transit time until the next process. Dry to Dry time: 85 seconds Line speed: 1500mm/min

0131
]

[Table 5] From the results in Table 5, samples S2, S3, T2, and T3 were subjected to the first humidity adjustment under an absolute humidity higher than the absolute humidity of the packaging work environment.
It was found that the dimensional elongation was larger compared to samples S4-9 and T4-9, and the effect of coating and drying was weakened. In addition, sample S1 whose second humidity adjustment time is shorter than 15 minutes
0 and T10, it was found that variations in dimensional characteristics increased with the passage of working time even within the same lot.

[0132] This revealed that samples S4-9 and T4-9 had excellent dimensional stability.

Example 7 Under the coating and drying conditions in Example 6, after the average temperature of the coated and drying surface was dried to 33° C., 5 seconds later, the coating was treated for 40 seconds according to drying conditions a to g shown in Table 5.

[0134]

[Table 6] Drying conditions A Dry with dry air at a dry bulb temperature of 35°C and relative humidity of 50%. Drying condition B Dry with dry air at a dry bulb temperature of 35°C and relative humidity of 22%. Drying condition C Dry with dry air at a dry bulb temperature of 80°C and relative humidity of 22%. Drying condition E Dry with dry air at a dry bulb temperature of 50°C and a relative humidity of 20%.

The processing conditions for cardboard were S5 and T5 in Example 1, and the dimensional stability was evaluated in the same manner as in Example 6, with the packaging conditions and coating drying conditions changed as shown in Table 7. . However, after coating and drying, each sample was conditioned for 1 hour at a temperature of 35° C. and a dew point of 15°, and the dew point was maintained at 16° or less until the end of the packaging process. The results are shown in Table 7.

[0136]

[Table 7] From the results in Table 7, all of them had high dimensional stability over the time required for the work, and in particular, there was little variation in the photosensitive material itself, giving good results.

Example 8 Sample No. of Example 1. For Samples 6 to 16, samples were prepared in the same manner as in Example 7, and the same treatments and evaluations were performed. As a result, it was found that the same results as in Example 7 were obtained.

[0138]

[Effects of the Invention] As explained in detail above, the present invention makes it possible to provide a photosensitive material that is excellent in antistatic ability, vacuum adhesion during working, and dimensional stability. Furthermore, a method for packaging the photosensitive material could also be provided.

Claims (5)

[Claims] Claim 1: In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one antistatic layer on a support, coating on one side of the support after completion of drying and coating on the opposite side. After drying or simultaneous application on both sides and drying, the humidity must be controlled for at least 1 hour at a temperature of 30°C or higher and a dew point of 16° or less, and the dew point must be maintained at 16° or less from the time both sides are coated and dried until the end of the packaging process. A silver halide photographic material characterized by: 2. The outermost layer on the side of the support having the silver halide emulsion layer contains regular silica having an average particle size of 4 μm or more, and the binder moisture content of the portion containing the outermost layer is 800 by weight. The silver halide photograph according to claim 1, wherein the time required for drying from % to 200% is 35 seconds or more, and the coating surface temperature of the outermost layer during that time is 19° C. or less. photosensitive material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion contained in the silver halide emulsion layer contains a tetrazolium compound or a hydrazine compound. 4. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one antistatic layer on a support, coating on one side of the support after drying and coating on the opposite side. After drying or simultaneous application on both sides and drying, the humidity must be controlled for at least 1 hour at a temperature of 30°C or higher and a dew point of 16° or less, and the dew point must be maintained at 16° or less from the time both sides are coated and dried until the end of the packaging process. A method for packaging a silver halide photographic material, characterized by: 5. In the packaging method of sealing the silver halide photographic light-sensitive material according to claim 1 in a sealed bag, the material is conditioned for at least 30 minutes at a humidity below the absolute humidity of the packaging work environment, and then the silver halide photographic material is sealed under the packaging process conditions. At least 1 piece of cardboard that has been conditioned for at least 15 minutes
A packaging method characterized by inserting more than one seed into a sealed bag and sealing the bag.