JP2724607B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material having improved film physical properties, and more particularly to a silver halide photographic light-sensitive material having excellent dimensional stability.

(Problems of the Prior Art) A silver halide photographic material generally comprises a layer having a hydrophilic colloid such as gelatin as a binder on at least one side of a support. Such a hydrophilic colloid layer has a disadvantage that it easily expands and contracts with changes in humidity and temperature.

The dimensional change of the photographic material due to the expansion and contraction of the hydrophilic colloid layer is extremely important in a photographic material for printing which requires the reproduction of a halftone image or a precise line drawing for multicolor printing. Disadvantages.

Dimensional Stab with little dimensional change, that is, dimensional stability
U.S. Pat. No. 3201 discloses a technique for defining the thickness ratio between a hydrophilic colloid layer and a support in order to obtain a photographic material having excellent ility).
Japanese Patent Publication Nos. 39-4272 and 39-17 describe a technique for incorporating a polymer latex into a hydrophilic colloid layer.
No. 702, No. 43-13482, No. 45-5331, U.S. Pat.
No. 00, No. 2763625, No. 2772166, No. 2852386, No. 285
No. 3457, No. 3397988, No. 3411911, and No. 3411912. Further, the theoretical support of the above technology is described by JQ Umberger in Photographic Science and Engineering (Phot. Sci. And Eng.) (1957), pp. 69-73.

However, in the printing field where multicolor printing and precise line drawing reproduction are required, further improvement in dimensional stability is strongly desired. In particular, although the dimensional stability before and after the processing steps (development, fixing, washing with water, and drying) that a photographic film always experiences is important, a technique for incorporating a polymer latex cannot provide a sufficient improvement.

This is because during the treatment process, the support is stretched by water absorption,
This is because even after the subsequent drying step, the elongation of the base does not return to its original state until a long time elapses, and practically elongation remains.

Therefore, when the dimensions of the unprocessed film and the processed film are compared, the latter is often in an extended state.

The art describes this phenomenon as poor dimensional stability with processing, which is a particularly serious drawback in photographic light-sensitive materials for printing.

In order to improve the dimensional stability accompanying the development processing, Japanese Patent Application No. 62-94133 discloses a technique using a vinylidene chloride undercoat layer. However, even if this technique is used, the dimensional stability accompanying the development processing cannot be completely improved, and further improvement has been desired.

(Problems to be Solved by the Present Invention) A first object of the present invention is to provide a silver halide photographic material having excellent dimensional stability accompanying processing.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having excellent dimensional stability accompanying environmental changes.

(Means for Solving the Problems) These objects of the present invention are as follows: 1) A silver halide photographic material having a hydrophilic colloid layer containing a polymer latex on at least one side of a polyester support. When a compound represented by the following general formula (I) is contained in at least one hydrophilic colloid layer on a polyester support and coated and dried,
300% or less of moisture is dried at a relative humidity of 50% or less based on the dry weight of the binder contained in all the layers formed on the support, and the silver halide photographic material is dried at an absolute humidity of 1%.
% Silver halide photographic material, which is stored in an atmosphere of not more than 10%.

In the formula, R represents a hydrogen atom or an alkyl group, an aralkyl group, or an aryl group, and these groups may be substituted.

 n represents 0 or 1.

2) The silver halide photographic light-sensitive material as described in 1) above, wherein the support is made of a polyester containing 70 to 99.5% by weight of vinylidene chloride and is coated on both sides with a polymer layer having a thickness of 0.3 μm or less. Achieved by

Various attempts have been made to improve the dimensional stability associated with the development process, but it is significantly improved by controlling the drying and subsequent storage humidity of the silver halide photographic material. That was unpredictable.

It is necessary that the silver halide photographic light-sensitive material of the present invention be dried at a relative humidity of 50% or less based on a moisture content of 300% or less based on the dry weight of the binder and then stored at an absolute humidity of 1% or less.

At this time, in a normal silver halide photographic light-sensitive material, the reaction rate of a curing agent for crosslinking a binder is significantly reduced, so that the swelling ratio of a hydrophilic colloid layer does not reach a desired level, and drying in an automatic developing machine is performed. Inconveniences such as poor or poor passability, and insufficient film strength of the hydrophilic colloid layer, causing scratches during development processing, and in some cases, important images being scraped off and partially lost Occurs.

In order to solve these problems, even if a fixing solution containing a curing agent is used, the amount of the curing agent cannot be solved by an amount used for a usual hardening fixer. By using a large amount of the curing agent, the drying property can be improved, but on the contrary, a disadvantage that the curing agent is deposited is caused and the processed photosensitive material is contaminated.

Such disadvantage can be solved by using the compound represented by the general formula (I) of the present invention.

(Specific constitution of the invention) In general, a silver halide photographic light-sensitive material is coated on a polyester support with a hydrophilic colloid layer as a water-soluble coating solution and then dried.

In the present invention, when drying after coating with the hydrophilic colloid layer coating solution, 5% or less of water is
It is necessary to dry at a relative humidity of 0% or less.

Hydrophilic colloid layer coating solution is based on binder dry weight
In the case of containing more than 300% of moisture, in the present invention, it is necessary to dry at a relative humidity of 50% or less after the point where the moisture content becomes 300% in the latter half of drying.

When two or more hydrophilic colloid layers are applied and dried at the same time, the water content represents the sum of the moisture content of all layers, and the binder dry content represents the sum of the binder dry weight of all layers.

The relative humidity in the present invention is the ratio of the amount of water vapor contained in a certain volume to the amount of saturated water vapor of the air expressed as a percentage.

In the present invention, the temperature for drying water of 300% or less based on the dry weight of the binder is usually preferably in the range of 25 ° C to 50 ° C.

In the present invention, drying refers to reducing the water content until the surface of the light-sensitive material does not have tackiness, and preferably 15% or less, particularly 10% or less based on the dry weight of the binder. Means to reduce the water content.

In the present invention, the silver halide photographic light-sensitive material must be stored under conditions of an absolute humidity of 1% or less. Absolute humidity is defined as the ratio of the weight of water vapor in the air to the weight of air. For example, 1% absolute humidity is 50% absolute humidity at 25 ° C.
In addition, at 40 ° C., this corresponds to a relative humidity of about 21%.

To reduce the absolute humidity to 1% or less, for example,
A method is used in which a silver halide photographic light-sensitive material left in a humid atmosphere for a sufficient time is hermetically packaged with a moisture-proof packaging material. As another method, it is also possible to use a method in which the moisture content of the core and paper packaged together with the silver halide photographic light-sensitive material is reduced in advance, and the air in the package after sealing is reduced to an absolute humidity of 1% or less. it can.

It is also effective to sufficiently reduce the drying air humidity in the latter half of the coating and drying process, reduce the atmospheric humidity of the processing site after winding, and then seal and package with a moisture-proof packaging material. Further, a method of hermetically packaging a desiccant such as silica gel together with a silver halide photographic material is also effective.

The package for sealingly packing the silver halide photographic light-sensitive material of the present invention may have any shape as long as it can seal the silver halide photographic light-sensitive material, and the use of the light-sensitive material to be sealed and Various shapes of the package are conceivable depending on the shape. Usually, a packaging bag made by heat sealing is preferably used. The material of the packaging bag is a polyethylene film with low moisture permeability (usually polyethylene is made to contain carbon black, etc., so as to have a light-shielding property and to make the polyethylene surface slippery, etc.
(Containing a substance which does not adversely affect the photosensitive material).

Another preferred form is a packaging bag in which an aluminum thin film is laminated.

A preferred embodiment of these packaging bags is disclosed in
No. 6,754, JP-A-58-132555, JP-A-61-189936 and the like.

When the silver halide photographic light-sensitive material of the present invention is packaged in these packaging bags, the packaging may be performed under reduced pressure to reduce the air in the packaging bags. In any case, in the present invention, it is preferable that the photosensitive material is packaged and stored in a sealed form under an atmosphere having an absolute humidity of 1% or less.

The compound represented by formula (I) used in the present invention will be described.

In the formula, R represents a hydrogen atom or an alkyl group, an aralkyl group, or an aryl group, and these groups may be substituted. n represents 0 or 1.

More specifically, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
20 alkyl groups (eg, methyl group, ethyl group, etc.), aralkyl groups having 6-20 carbon atoms (eg, benzyl group, phenethyl group, etc.), and aryl groups having 5-20 carbon atoms (eg, phenyl group, naphthyl group, pyridyl group) And the like, and those groups may be substituted. Examples of the substituent include a sulfonic acid group, a hydroxyl group, a carboxyl group and the like.

 Particularly preferred as R is a hydrogen atom.

 n represents 0 or 1.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

It is desirable to select an optimal amount of the compound represented by the general formula (I) depending on the kind of the compound example, the kind of gelatin, etc., and 0.5 × 10 ⁻³ to 50 × 10 ⁻³ per 100 g gelatin.
× 10 ^-3 mol is appropriate, and preferably 2 × 10 ^{-3 to} 20 × 10
^-3 mol.

The compound represented by formula (I) used in the present invention is contained in at least one of hydrophilic colloid layers such as a silver halide emulsion layer, a back layer, a protective layer, and an intermediate layer.

In the silver halide emulsion layer and / or other photographic constituent layers, the compound represented by formula (I) may be used in combination with a gelatin hardener commonly used in the art. Examples of such curing agents include formaldehyde, aldehyde compounds such as glutaraldehyde, diacetyl,
Ketone compounds such as cyclopentanedione, bis (2
-Chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other U.S. Pat. Nos. 3,288,775
No. 2,732,303, UK Patent No. 974,723, No. 1,16
Compounds having a reactive halogen as shown in 7,207 and the like, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3-5-triazine, and other U.S. Patent Nos. 3,635,718 and 3,232,763 No.
3,490,911, 3,642,486, compounds having a reactive olefin such as those shown in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent Nos. 2,732,316 and 2,586,168. N-methylol compounds as described in U.S. Pat.
No. 7,017,280, U.S. Pat.No. 3,017,280, Aziridine compounds as shown in U.S. Pat.No. 2,983,611, U.S. Pat.Nos. 2,725,294, 2,725,295, etc. Acid derivatives, carbodiimide-based compounds as shown in U.S. Pat.No. 3,100,704, epoxy compounds as shown in U.S. Pat.No. 3,091,537, U.S. Pat.
Nos. 313 and 3,543,292, isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or chromium chloride as an inorganic hardener. Van, zirconium sulfate and the like.

The hydrophilic colloid layer of the photographic light-sensitive material of the present invention includes a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer and the like, and a hydrophilic colloid is used for these layers. Gelatin is most preferred as the hydrophilic colloid.As gelatin, any of those generally used in the art such as so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, and gelatin derivatives and denatured gelatin can be used. Among them, lime-processed gelatin and acid-processed gelatin are preferably used.

In addition to gelatin, proteins such as colloidal albumin and casein; cellulose compounds such as carboxymethylcellulose and hydroxyethylcellulose; bran derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N-vinyl A pyrrolidone polyacrylic acid copolymer, polyacrylamide or a derivative or partial hydrolyzate thereof can be used. If desired, mixtures of two or more of these colloids can be used.

The polymer latex used in the present invention has an average particle size.
20mμ ~ 200mμ aqueous dispersion of water-insoluble polymer, the preferred amount is gelatin used as a binder
The dry weight ratio with respect to 1.0 is preferably 0.01 to 1.0, and particularly preferably 0.1.
1 to 0.8.

Preferred examples of the polymer latex used in the present invention are alkyl esters of acrylic acid, hydroxyalkyl esters or glycidyl esters, or
Having an alkyl ester of methacrylic acid, a hydroxyalkyl ester, or a glycidyl ester as a monomer unit, and having an average molecular weight of 100,000 or more, particularly preferably 30
10,000 to 500,000 polymers, and specific examples are shown by the following formula.

Furthermore, regarding polymer latex,
45-5331, U.S. Pat.Nos. 2,852,386, 3,062,674, and 3411.
Nos. 911 and 3411912 can be referred to.

The polymer latex used in the present invention is contained in at least one of hydrophilic colloid layers such as a silver halide emulsion layer, a back layer, a protective layer, and an intermediate layer.

The present invention is particularly effective in a super-high contrast material containing a hydrazine derivative.

Regarding such a hydrazine derivative-containing ultra-high contrast material and an image forming method using the same, US Pat. No. 4,224,401
Nos. 4,168,977, 4,166,742, 4,241,164
No. 4,272,606, JP-A-60-83028, JP-A-60-2186
No. 42, No. 60-258537, No. 61-223738 and the like.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (Q).

In the formula, A represents an aliphatic group or an aromatic group, B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
A carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfanyl group or a heterocyclic group, wherein X and Y are both hydrogen atoms or one of them is a hydrogen atom and the other is substituted or Represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

Representative compounds among the compounds represented by formula (Q) are shown below.

Further, the present invention provides a photosensitive material containing a tetrazolium compound in a PQ type containing a relatively high concentration of sulfite or
The effect can also be exerted in a method of obtaining high contrast by processing with an MQ type developer. The image forming method using a tetrazolium compound is described in JP-A-52-18317, JP-A-53-17719 and JP-A-53-17720.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-soluble silver salt (eg, silver nitrate) solution and a water-soluble halogen salt (eg, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing.

As silver halide, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used, and the grain morphology and size distribution are not particularly limited.

The silver halide emulsion layer can contain a film physical property improving agent such as a photosensitive silver halide, a chemical sensitizer, a spectral sensitizer, an antifoggant, a surfactant, and a thickener. These are described in Research Disclosure, 176
17643 (December 1978), and JP-A-52-10813
Nos. 0, 52-114328, 52-121321, 53-3217
And JP-A-53-44025 can be referred to.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412.

The surface protective layer is a layer having a thickness of 0.3 to 3 μm, particularly 0.5 to 1.5 μm, using a hydrophilic colloid such as gelatin as a binder, and includes therein a matting agent such as fine particles of polymethyl methacrylate, colloidal silica, and If necessary, the composition contains a thickener such as potassium polystyrene sulfonate, a gelatin hardener, a surfactant, a sliding agent, a UV absorber and the like.

The back layer is a layer using a hydrophilic colloid such as gelatin as a binder, is non-photosensitive, and may have a single-layer structure or a multilayer structure having an intermediate layer, a protective layer, and the like.

The thickness of the back layer is 0.1μ to 10μ, in which gelatin hardeners, surfactants, matting agents, colloidal silica, sliding agents, UV absorption as required, as well as silver halide emulsion layers and surface protective layers. Agents, dyes, thickeners and the like.

The method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer. Typically, a photographic material of a type using silver halide as a photosensitive component, for example, a photosensitive material for printing, X
-It can be used as a light-sensitive material for rays, a general negative light-sensitive material, a general reversal light-sensitive material, a general positive light-sensitive material, a direct positive light-sensitive material and the like. The effect of the present invention is particularly remarkable in a photosensitive material for printing.

There are no particular restrictions on the exposure method, development processing method, and the like of the photosensitive material of the present invention. For example, JP-A-52-108130,
Reference can be made to the specifications of JP-A Nos. 52-114328 and 52-121321 and the descriptions in the above-mentioned Research Disclosure Magazine. JP-A-60-258537 and U.S. Pat.
As described in No. 9, the development speed can be increased by adding amines to shorten the development time.

The vinylidene chloride copolymer in the present invention is 70 to 9
A copolymer containing 9.5% by weight, preferably 85 to 99% by weight, of vinylidene chloride; a copolymer comprising vinylidene chloride / acrylate / vinyl monomer having an alcohol in a side chain described in JP-A-51-135526. Polymer, U.S. Patent 2,852,37
A copolymer of vinylidene chloride / alkyl acrylate / acrylic acid described in No. 8, a copolymer of vinylidene chloride / acrylonitrile / itaconic acid described in US Pat. No. 2,698,235, and a vinylidene chloride / alkyl acrylate / itacon described in US Pat. No. 3,788,856 And copolymers composed of acids. The following are specific examples of the compound.

 All figures in parentheses indicate weight ratios.

Vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (83: 12: 5) copolymer Vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (83: 10: 8) copolymer Vinylidene chloride: hydroxydiethyl methacrylate (92: 8) )) Copolymer of vinylidene chloride: methyl methacrylate: acrylonitrile (90: 8: 2) Copolymer of vinylidene chloride: butyl acrylate: acrylic acid (9
4: 4: 2) copolymer vinylidene chloride: butyl acrylate: itaconic acid (7
5: 20: 5) copolymer vinylidene chloride: methyl acrylate: itaconic acid (9
0: 8: 2) Copolymer of vinylidene chloride: methyl acrylate: methacrylic acid (93: 4: 3) Vinylidene chloride: itaconic acid monoethyl ester (96:
4) Copolymer of vinylidene chloride: acrylonitrile: acrylic acid (96:
3.5: 1.5) copolymer vinylidene chloride: methyl acrylate: acrylic acid (9
0: 5: 5) vinylidene chloride: ethyl acrylate: acrylic acid (9
2: 5: 3) copolymer vinylidene chloride: methyl acrylate: 3-chloro-2-
Hydroxypropyl acrylate (84: 9: 7) copolymer Vinylidene chloride: methyl acrylate: N-ethanolacrylamide (85: 10: 5) copolymer Vinylidene chloride copolymer of the present invention is coated on a polyester support. As a method, a solution in which these polymers are dissolved in an appropriate organic solvent, or an aqueous dispersion is generally known as a coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, It can be applied by a wire bar coating method, a gravure coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294. In addition, there is a so-called extrusion coating method in which a molten polymer is made to flow into a film and flows down onto a moving polyester, and is bonded by pressure simultaneously with cooling.

Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma for the surface of the polyester support to further improve the adhesive force between the polyester support and the polymer layer Processing such as treatment, high-pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment may be performed.

In order to firmly adhere the polymer layer used in the present invention to a polyester base, US Pat. No. 3,245,937
No. 3,143,421, No. 3,501,301, No.3,271,178, including phenol, resorcinol, o-cresol, m-cresol, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, foamed water chloral,
It is necessary to add a polyester swelling agent such as benzyl alcohol. As these swelling agents, resorcin is preferably used, but resorcin often has a drawback of causing spot failure in the manufacturing process.

A particularly preferred method for avoiding such disadvantages is to apply a polymer layer to be used in the present invention after glow discharge treatment of the surface of the polyester support.

The glow discharge treatment in the present invention may be any method known in the art, for example, Japanese Patent Publication No. 35-7578 and No. 36-10.
No. 336, No. 45-22004, No. 45-22005, No. 45-24040
Nos. 46-43480, U.S. Pat.Nos. 3,057,792 and 3,057,79
No. 5, 3,179,482, 3,288,638, 3,309,299,
3,424,735, 3,462,335, 3,475,307, 3,7
Nos. 61,299, UK Patent 997,093, JP-A-53-129262 and the like can be used.

The pressure during glow discharge is 0.005 to 20 Torr, preferably 0.0
2-2 Torr is appropriate. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow, sparks are likely to occur, it is dangerous, and there is a risk of destroying the workpiece. The discharge is generated by applying a high voltage between metal plates or metal rods arranged at one or more spaces in a vacuum tank. This voltage can take various values depending on the composition and pressure of the atmosphere gas. However, in the above-mentioned pressure range, a stable fixing glow discharge occurs between 500 and 5000 V. A particularly preferred voltage range for improving the adhesion is 2000-4000V.

Also, as seen in the prior art as the discharge frequency,
A DC to several 1000 MHz, preferably 50 Hz to 20 MHz is appropriate. Regarding the discharge treatment strength, 0.01 KV · A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.05 KV · A · min / m ^{2 to 1} KV · A · Min / m ² is appropriate.

The thickness of the vinylidene chloride copolymer layer in the present invention is preferably large in order to suppress the elongation of the base due to water absorption during the development step. However, if the thickness is too large, the adhesion to the silver halide emulsion layer is disadvantageously caused.

Therefore, the thickness is 0.3 μm or more and 5 μm or less, preferably 0.5 μm or more and 2.0 μm or less.

In the present invention, polyester is a polyester containing aromatic dibasic acid and glycol as main constituents. Representative dibasic acids are terephthalic acid, isophthalic acid, p
-Β-oxyethoxybenzoic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenylenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like. And glycols such as ethylene glycol, propylene glycol, butanediol, neopentylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4
-Bisoxyethoxybenzene, bisphenol A, diethylene glycol, polyethylene glycol and the like.

Of the polyesters composed of these components, polyethylene terephthalate is the most convenient in terms of availability.

The thickness of the polyester is not particularly limited, but is about 12μ.
Those having a size of about 200 μm, preferably about 40 μm to 180 μm are advantageous in terms of ease of handling and versatility. In particular, those biaxially stretched and crystallized are advantageous in terms of stability, strength and the like.

In order to improve the adhesive strength between the polymer layer and the emulsion layer, a layer having adhesiveness to either of them can be provided as an undercoat layer. Further, in order to further improve the adhesiveness, the surface of the polymer layer may be subjected to conventional pretreatment such as corona discharge, ultraviolet irradiation, and flame treatment.

 Hereinafter, the present invention will be further described with reference to Examples.

(Comparative Example) Among the undercoat supports disclosed in Example 1 of JP-A-60-26944, one of the supports using the second undercoat composition 1 was coated with one of the following halogens in order from the support side. Silver halide emulsion layer,
The protective layer 1 was applied and dried under the conditions shown in Table 1. Next, a back layer and a protective layer 2 are applied to the opposite surface,
It dried under the conditions of Table 1.

(1) Silver halide emulsion layer formulation In a gelatin aqueous solution kept at 50 ° C., 2 ×
In the presence of 10 ^-5 mol of rhodium chloride, an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to prepare a silver chlorobromide monodispersed emulsion having an average particle size of 0.2μ. did. (Cl composition 95 mol%) This emulsion was desalted by flocculation method.
1mg thiourea dioxide and 0.6mg per mole of silver
Of chloroauric acid was added, and the mixture was aged at 65 ° C. until the maximum performance was obtained, and fog was generated.

 The following compounds were further added to the emulsion thus obtained.

KBr 20 mg / m ² polystyrene sulfonic acid sodium salt 40 mg / m ² 2,6-dichloro-4-hydroxy-1,3,5 - triazine sodium salt 30 mg / m ² The coating liquid and the coating silver amount 3.5 mg / m ² Was applied.

(2) Protective layer 1 formulation Gelatin 1.5 g / m ² SiO ₂ fine particles (average particle size 4 μ) 50 mg / m ² Dodecylbenzenesulfonic acid sodium salt 50 mg / m ² 5-nitroimidazole 15 mg / m ² 1,3-divinylsulfonyl-2-propanol 50 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potadium salt 2 mg / m ² Polymer 2 (average particle size 0.06 μ) 300 mg / m ² (3) Back layer formulation Gelatin 2.5g / m ² 1,3-divinylsulfonyl-2-propanol 150 mg / m ² polymer 2 (average particle size 0.06 μ) 900 mg / m ² dihexyl α-sulfosacnate sodium salt 10 mg / m ² dodecylbenzenesulfonic acid sodium salt 35 mg / m ² (4) Protective layer 2 formulation Gelatin 0.8 g / m ² Polymethyl methacrylate fine particles (average particle size 3 μ) 20 mg / m ² Dihexyl α sulfosacnate sodium salt 10 mg / m ² Dodecylbenzenesulfonic acid sodium salt 10 mg / m ² Sodium acetate 40 mg / m ² After coating and drying, moisture-proof bags were packaged under the conditions shown in Table 1 to obtain samples (1) to (11). JP-A-61-18 as a moisture-proof bag
Invention 8 disclosed in Example 1 of No. 9936 was used.

After leaving the sample sealed in the moisture-proof bag for 2 weeks in an atmosphere of 25 ° C., the following method (1) dimensional change due to treatment,
(2) Wet film strength and (3) Drying property by an automatic developing machine were evaluated.

(1) Evaluation method of dimensional change due to treatment Drill two holes of diameter 8mm at 200mm intervals on the sample,
After standing in a room at 25 ° C. and 30% RH, the distance between the two holes was accurately measured using a pin gauge with an accuracy of 1/1000 mm. The length at this time is Xmm. Then, with an automatic developing machine, development,
After fixing, washing and drying, the size 5 minutes later is defined as Ymm. Dimensional change rate (%) due to processing Was evaluated.

In the industry, it is considered that there is no practical problem if the dimensional change rate is 0.01% or less.

The development was carried out using a FG-660 automatic developing machine manufactured by Fuji Photo Film Co., Ltd., and GRD-1 and GRF-1 manufactured by Fuji Photo Film Co., Ltd. under processing conditions of 38 ° C. for 20 seconds. The drying temperature at that time was 45 ° C.

(2) Method of evaluating wet film strength After immersing a wet film strength sample in distilled water at 25 ° C for 5 minutes, the sample was pressed against the sample film surface with a needle with a 0.4 mm radius steel ball attached to the tip, and a speed of 10 mm / sec. The load of the needle was continuously changed while moving as described above, and the load (g) when the film was broken (that is, a scratch was generated on the sample film surface) was measured.

(3) Evaluation method of drying property by automatic development processing When 10 sheets of a film of 50.8 × 61 cm ² were continuously processed in an environment of 30 ° C. and 80% RH, it was determined from which sheet the film became undried.

The determination of the dry state was made by touching the film surface with a hand to determine the wetness.

 The absolute humidity in the moisture-proof bag of this sample was measured.

For the measurement, the relative humidity was measured under a temperature condition of 25 ° C., and the absolute humidity was obtained using an air chart.

For measurement of relative humidity, use a thermo-hygrometer MODEL HN-U ₂ HUMI-T
The relative humidity was measured using an EMP RECODER (manufactured by Chino Corporation) (Sensor HN-L20 (manufactured by Chino Corporation)), and the results were converted to absolute humidity using a psychrometric chart.

(Example-1) Samples (101) to (109) were prepared in the same manner as in the comparative example, except that the hardener in the silver halide emulsion layer formulation, the protective layer 1 formulation, and the back layer formulation in the comparative example was changed as shown in Table-2. made.

In the same manner as in the comparative example, (1) a dimensional change accompanying the treatment,
(2) Strengthening of wet film, and (3) Drying property by processing with an automatic developing machine were evaluated.

(Example-2) Silver halide emulsion layer, protective layer 1, back layer, protective layer 2
Samples (201) to (211) were prepared in the same manner as in Comparative Example except that the following formulation was used, and the same evaluation was performed.

(1) Formulation of silver halide emulsion layer Emulsion A was prepared by the following method using the following solutions I, II and III.
Was adjusted.

Solution I: 300 ml of water, 9 g of gelatin II solution; 100 g of AgNO ₃ , 400 ml of water III solution: 37 g of NaCl, 0.66 mg of (NH ₄ ) ₃ RhCl ₆ , 400 ml of water Simultaneously with solution II and solution III in solution I kept at 40 ° C It was added at a constant rate. After removing soluble salts from the emulsion by a conventional method well known in the art, gelatin was added thereto, and 6-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene and 4-hydroxy −5,6-trimethylene-1,
3,3a, 7-Tetraazaindene was added.

This emulsion was a monodispersed emulsion having an average grain size of 0.15 μm, and the amount of gelatin contained per kg of the emulsion was 60 g.

 The following compounds were added to the emulsion thus obtained.

Polystyrenesulfonic acid sodium salt 10 mg / m ² Compound example I-1) 34.5 mg / m ² Polymer 2 (average particle size 0.06 μ) 500 mg / m ² The coating solution thus obtained was applied so that the applied silver amount was 3 g / m ² .

(2) Formulation of protective layer 1 Gelatin 1.5 g / m ² Fine particles of polymethyl methacrylate (average particle size 3 μ) 50 mg / m ² Dodecylbenzenesulfonic acid sodium salt 25 mg / m ² Dihexyl α-sulfosacnate sodium salt 10 mg / m ² N-perfluorooctanesulfonyl N-propylglycine potashum salt 2 mg / m ² Polystyrenesulfonic acid sodium salt 3 mg / m ² Polymer 2 ( Average particle size 0.06μ) 200mg / m ² Colloidal silica 350mg / m ² Lipoic acid 8mg / m ² (3) Back layer formulation Gelatin 2g / m ² Dihexyl α sulfosacnate sodium salt 20 mg / m ² Sodium dodecylbenzenesulfonate 30 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² Compound example I-1) 34.5 mg / m ² Polymer 2 (average particle size 0.06 μ) 200 mg / m ² (4) protective layer 2 formulation gelatin 1 g / m ² polymethyl methacrylate fine particles (average particle size 3μ) 40 mg / m ² dihexyl sulfosacnate sodium salt 10 mg / m ² dodecylbenzenesulfonic acid sodium salt 30 mg / m ² polystyrene acid sodium salt 25 mg / m ² sodium acetate 30 mg / m ² Example 3 Samples (301) to (310) were prepared in the same manner as in Example 1 except that the following support was used, and the same evaluation was performed.

 The results are shown in Table 4.

Four semicircular rod electrodes having a cross section of 3 cm in diameter and a length of 40 cm were fixed in an insulating plate shape at intervals of 10 cm. The electrode plate was fixed to a vacuum tank, and a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm and a width of 30 cm was run at a speed of 20 m / min on a rod facing the electrode surface at a distance of 15 cm from the electrode surface. Immediately before the film passed over the electrode, a heating roll with a temperature controller having a diameter of 50 cm was set at 120 ° C. and the heating roll was arranged such that the film was in contact with the film for 3/4 turn. The glow discharge was performed by applying a voltage of 2000 V to the electrodes while maintaining the inside of the tank at 0.1 Torr. At this time, the electrode current was 0.5A. At this time, the PET support has been subjected to treatment at 0.125 KVA min / m ² . In this way, vinylidene chloride / methyl acrylate / acrylic acid =
90: 5: 5 wt% copolymer aqueous dispersion 0.5μ
And dried at a temperature of 120 ° C.

Furthermore, 20 ml of the following prescription coating solution is applied as a second layer of undercoating
/ m ^2, and dried at a temperature of 160 ° C.

(1) Undercoat second layer formulation Gelatin 1.0 part by weight Reaction product of epichlorohydrin, a polyamide composed of diethylenetriamine and apicinic acid 0.07 part by weight Saponin 0.01 part by weight Water added to 100 parts by weight Example 4 Example 4 was repeated except that the following silver halide emulsion layer formulation was used.
Samples (401) to (410) were prepared in the same manner as in No. 3, and the same evaluation was performed. At this time, the following developer formulation was used. The results are shown in Table-5.

(1) Silver halide emulsion layer formulation A silver chlorobromide emulsion containing 1 × 10 ^-5 mol of rhodium per Ag / mol (Br / mol%, average grain size 0.2 μm) was used as a stabilizer without chemical ripening. 4-hydroxy-6-methyl-1,3,
3a, 7-Tetrazaindene was added. Add the tetrazolium salt to this emulsion Was added at 5 × 10 ^-3 mol / Ag / mol.

Further, as a polymer latex, Polymer 1 was added to the emulsion so as to be 1.4 g / m ² . As the gelatin hardener, the same compound as in Example 1 was used. This emulsion was coated 3.
The coating was performed so that 9 g / m ² and the amount of gelatin became 3.1 g / m ² .

(2) Formulation of developing solution Ethylenediaminetetraacetic acid disodium salt (dihydrate) 0.75 g anhydrous potassium sulfite 51.7 g anhydrous potassium carbonate 60.4 g hydroquinone 15.1 g 1-phenyl-3-pyrazolidone 0.51 g sodium bromide 2.2 g 5-methylbenz Triazole 0.124 g 1-Phenyl-5-mercaptotetrazole 0.018 g 5-Nitro-indazole 0.160 g Diethylene glycol 98 g 1 with water (ph = 10.5) Example-5 A sample 501 was prepared in exactly the same manner as in the sample 101 except that a layer having the following composition was provided as the second undercoat layer of the sample 101 of the example 101.

 Sample 501 showed good results as well as sample 101.

Binder; gelatin 1 g / m ² polymer latex 0.16 g / m ²

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a polymer latex on at least one side of a polyester support, on the polyester support, represented by the following general formula (I): When at least one hydrophilic colloid layer contains the compound to be coated, and is coated and dried, a water content of 300% or less based on the dry weight of the binder contained in all the layers formed on the support is 50% or less. A silver halide photographic material characterized by being dried at a humidity and storing the silver halide photographic material in an atmosphere having an absolute humidity of 1% or less. In the formula, R is a hydrogen atom or an alkyl group, an aralkyl group,
Represents an aryl group, and those groups may be substituted. n represents 0 or 1. 2. The polyester according to claim 1, wherein said support is a polyester comprising a copolymer containing 70 to 99.5% by weight of vinylidene chloride and coated on both sides with a polymer layer having a thickness of 0.3 μ or more. The silver halide photographic light-sensitive material as described above.