JP3314194B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved drying properties after development processing.

In recent years, there has been a demand for shortening the development processing time of silver halide photographic materials. In order to shorten the development processing time, it is effective to improve the drying property of the silver halide photographic light-sensitive material to shorten the drying time. As a means for improving the drying property, there is a method of reducing the amount of a binder in a silver halide photographic light-sensitive material. However, this method causes problems such as a decrease in mechanical strength of the silver halide photographic light-sensitive material and blackening of abrasion. Abrasion blackening is a phenomenon in which, when a silver halide photographic light-sensitive material before development processing is handled, when the film surface is rubbed, this part blackens into a scratch after development processing. Further, the roller mark is a phenomenon in which, when the silver halide photographic light-sensitive material is subjected to automatic development processing, pressure is applied to the silver halide photographic light-sensitive material due to minute unevenness of the roller, and black spot-like density unevenness occurs. Both abrasion blackening and roller marks significantly reduce the commercial value of silver halide photographic materials.

As another means of improving the drying property, it is effective to increase the amount of a hardener added to a silver halide photographic material. In this method, the swelling of the silver halide photographic light-sensitive material during the development processing is reduced, so that the drying property is improved. However, in this method, problems such as a delay in development progress, a change in photographic properties, and a residual silver and a residual color due to a delay in fixing occur, and a sufficient improvement in drying properties cannot be achieved.

In the case where the silver halide emulsion layer is a silver halide photographic light-sensitive material on one side of a support (hereinafter referred to as "one-sided light-sensitive material"), the non-light-sensitive hydrophilic colloid layer on the back surface is removed. Alternatively, by making the binder of the non-photosensitive layer on the back surface a hydrophobic binder, the drying property is improved. However, in this method, the curl of the silver halide photographic light-sensitive material is significantly deteriorated and cannot be put to practical use.

In general, a silver halide photographic material has a photographic layer containing a hydrophilic colloid as a binder, so that the dimensional change of the silver halide photographic material due to the expansion and contraction of the photographic layer due to the change of temperature and humidity. It has the drawback of getting up. This dimensional change of the silver halide photographic light-sensitive material is a very serious disadvantage in the silver halide photographic light-sensitive material for printing which requires reproduction of halftone images and precise line drawings for multicolor printing. Become. Conventionally, various means have been known for improving the dimensional stability of a silver halide photographic light-sensitive material. For example, U.S. Pat. No. 320125 discloses a technique for defining a thickness ratio between a hydrocolloid layer and a support.
No. 4272, No. 39-17702, No. 43-1348
No. 2, No. 45-5331, U.S. Pat.
No. 2763625, No. 2772166, No. 2852
No. 386, No. 2853457, No. 3397988,
Nos. 3411911 and 3411912 describe a method of adding a polymer latex to a hydrocolloid photographic layer. Certainly, by using these techniques, the dimensional stability of the silver halide photographic light-sensitive material due to changes in temperature and humidity can be improved. However, these techniques cannot prevent a dimensional change due to the development processing of a silver halide photographic light-sensitive material. This "dimension change due to development processing" is a phenomenon in which the dimensions of a silver halide photographic light-sensitive material change before and after the development processing, and is a very serious defect particularly in a silver halide photographic light-sensitive material for printing.

A second cause of the dimensional change due to the development processing is that the dimensions of the silver halide photographic light-sensitive material irreversibly change due to the wet state during the development processing and the high temperature and low humidity conditions in the drying step. For this reason, the length of the silver halide photographic light-sensitive material may change before and after processing. As means for reducing this dimensional change, Japanese Patent Application Laid-Open No.
JP-A Nos. 40 and 1-270046 disclose a technique in which a drying step after coating is performed at a low humidity during the production of a silver halide photographic light-sensitive material, followed by storage at a low humidity. Certainly, the dimension caused by the above-mentioned cause is improved by this method, and dimensional stability which does not hinder practical use can be obtained. However, the dimensional change cannot be reduced to zero by using the above-mentioned means, and when extremely high dimensional stability is required, the above-described means alone is not sufficient.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material having good drying properties after development processing. A second object of the present invention is to provide a silver halide photographic light-sensitive material having improved curl. A third object of the present invention is to provide a silver halide photographic material having improved dimensional stability.

[0008]

The object of the present invention is to provide a support having at least one silver halide emulsion layer having a hydrophilic colloid as a binder on one surface thereof, wherein the silver halide emulsion layer of the support is coated. In a silver halide photographic material having at least one non-photosensitive hydrophilic colloid layer on the surface opposite to the surface on which the silver halide emulsion layer is provided, the surface opposite to the surface opposite to the surface provided with the silver halide emulsion layer Wherein the weight ratio of the total amount of the hydrophilic colloid is 0.3 or more, and moisture is permeable to the surface on which the non-photosensitive hydrophilic colloid layer is coated, at a position separated from the support from the non-photosensitive hydrophilic colloid layer. Coefficient is 0.10 × 10
^This was achieved by a silver halide photographic material characterized by having a hydrophobic polymer layer of at least ^-10 g · cm / cm ² / sec / cmHg.

First, the non-photosensitive hydrophilic colloid layer (hereinafter referred to as a back layer) of the present invention will be described. The back layer of the present invention is a layer containing a hydrophilic colloid as a binder, but as a hydrophilic colloid used in the back layer, a binder for a photographic layer on the side on which a silver halide emulsion layer is coated from the viewpoint of curling is used. Those having a similar moisture absorption rate and moisture absorption rate are preferred. The most preferred hydrophilic colloid used as the binder in the back layer of the present invention is gelatin. As the gelatin, any of those generally used in the art such as so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, and modified gelatin can be used. Of these gelatins,
Most preferably used are lime-processed gelatin and acid-processed gelatin.

As hydrophilic colloids other than gelatin, proteins such as colloidal albumin and casein, sugar derivatives such as agar, sodium alginate and starch derivatives, cellulose compounds such as carboxymethylcellulose and hydroxymethylcellulose, polyvinyl alcohol and poly-N
-Synthetic hydrophilic compounds such as vinylpyrrolidone and polyacrylamide. In the case of a synthetic hydrophilic compound, other components may be copolymerized. However, if the amount of the hydrophobic copolymer component is too large, the moisture absorption rate and moisture absorption rate of the back layer become small, which is inappropriate from the viewpoint of curling. These hydrophilic colloids may be used alone or in combination of two or more.

In the back layer of the present invention, other than the binder,
A photographic additive such as a matting agent, a surfactant, a dye, a crosslinking agent, a thickener, a preservative, a UV absorber, and inorganic fine particles such as colloidal silica may be added. Regarding these additives, for example, the description in Research Disclosure Magazine, Vol. 176, 17643, December 1978 can be referred to.

The back layer of the present invention may further contain a polymer latex. The polymer latex used in the present invention is an aqueous dispersion of a water-insoluble polymer having an average particle size of 20 μm to 200 μm. Is 0.1 to 0.8. Preferred examples of the polymer latex used in the present invention include acrylic acid alkyl ester, hydroxyalkyl ester or glycidyl ester, or methacrylic acid alkyl ester, hydroxyalkyl ester, or glycidyl ester as a monomer unit and have an average molecular weight of 10 It is a polymer of 10,000 or more, particularly preferably 300,000 to 500,000, and a specific example is shown by the following formula.

[0013]

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The back layer of the present invention may be a single layer or two or more layers. Although the thickness of the back layer of the present invention is not particularly limited, it is preferably about 0.2 μm to 20 μm, particularly preferably 0.5 μm to 10 μm from the viewpoint of curling. When the back layer is composed of two or more layers, the sum of the thicknesses of all the back layers is
It is the thickness of the back layer of the silver halide photographic light-sensitive material of the present invention.

The method for applying the back layer of the present invention is not particularly limited. Conventionally, a known method for coating a hydrophilic colloid layer of a silver halide photographic light-sensitive material can be used. For example, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or US Pat.
The extrusion coating method using a hopper described in U.S. Pat. No. 6,681,294, or U.S. Pat.
The multi-layer simultaneous coating method described in 508947 and 2761791 can be used.

Next, the hydrophobic polymer layer (polymer layer) of the present invention will be described. The hydrophobic polymer layer of the present invention is hydrophobic and has a moisture permeability coefficient of 0.1 × 10 ⁻¹⁰ g · cm / cm ² / sec / c.
There is no particular limitation as long as it is at least mHg. However, the term "hydrophobic" as used herein means that the water content at the end of the washing step in the developing treatment of the hydrophobic polymer layer is 0.5% or less.
Specific examples of the polymer layer binder include polystyrene, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, butadiene rubber, chloroprene rubber, rubbers such as natural rubber, polymethyl methacrylate, polyethyl acrylate Esters of acrylic acid or methacrylic acid, such as polyester resins such as polyethylene phthalate, nylon 6, nylon 66
And water-insoluble polymers such as silicone resins and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. These may be used alone or in combination of two or more.

The polymer layer of the present invention may contain, if necessary, a photographic additive such as an inorganic fine particle such as a matting agent, a surfactant, a dye, a slipping agent, a crosslinking agent, a thickener, a UV absorber, and colloidal silica. May be added. These additives are also described in Research Disclosure Magazine, Vol.
The description in Section 43 (December 1978) can be referred to.

The polymer layer of the present invention may be a single layer or two or more layers. The thickness of the polymer layer of the present invention is not particularly limited. However, when the thickness of the polymer layer is too small, the water resistance of the polymer layer becomes insufficient, and the back layer swells in the processing solution, which is inappropriate. Conversely, if the thickness of the polymer layer is too large, water vapor transmission through the polymer layer becomes insufficient, and moisture absorption and desorption of the hydrophilic colloid layer of the back layer is inhibited, resulting in poor curling. Of course, the thickness of the polymer layer also depends on the physical properties of the binder used. Therefore, the thickness of the polymer layer needs to be determined in consideration of both. The preferred thickness of the polymer layer is 0.05 to 10 μm, depending on the binder type of the polymer layer.
m, more preferably in the range of 0.1 to 5 μm. When the polymer layer of the present invention comprises two or more layers, the sum of the thicknesses of all the polymer layers is defined as the thickness of the polymer layer of the silver halide photographic light-sensitive material of the present invention.

The method for applying the polymer layer of the present invention is not particularly limited. After coating and drying the back layer, a polymer layer may be coated on the back layer and then dried, or the back layer and the polymer layer may be simultaneously coated and then dried. The polymer layer may be dissolved in a solvent for the binder of the polymer layer and applied in a solvent system, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

The support for the silver halide photographic light-sensitive material of the present invention is not particularly limited, and those generally used in the art can be used. Preferred specific examples of the support include polyethylene terephthalate.

In general, when producing a silver halide photographic light-sensitive material,
A hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer, and a protective layer is coated on a support after water-soluble coating and dried. In the present invention, when applying and drying the coating liquid for the hydrophilic colloid layer, it is necessary to dry the water of 300% or less based on the dry amount of the binder under the condition of the relative humidity of 50% or less. When the coating liquid for the hydrophilic colloid layer contains more than 300% of water based on the dry weight of the binder, the present invention uses the relative humidity of 50% or less after the point where the water content becomes 300% in the latter half of the drying. It is necessary to dry. When two or more hydrocolloid layers are applied and dried at the same time, the amount of moisture represents the sum of the moisture of all the applied layers, and the binder dry amount represents the sum of the binder dry amounts of all the layers. The relative humidity of 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 moisture 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 reducing the water content.

In the present invention, the silver halide photographic light-sensitive material must be stored under conditions of an absolute humidity of 12 g / m ³ or less. Here, "storage" refers to placing the photosensitive material under the conditions of the present invention for a period until a general user uses the photosensitive material. For this purpose, for example, a method is used in which a silver halide photographic light-sensitive material which has been left in this temperature and humidity atmosphere for a sufficient time is hermetically packaged with a moisture-proof packaging material. As another method, the moisture content of the core and paper packaged together with the silver halide photographic light-sensitive material is reduced in advance, and the temperature and humidity in the package after the packaging is sealed are adjusted to an absolute humidity of 12 g / m ³ or less. Can also be used. 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 hermetically packaging the silver halide photographic material of the present invention may have any shape as long as it can seal the silver halide photographic material. Various package shapes are conceivable depending on the use and shape of the material. 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 contains carbon black, etc., which has a light-shielding property and has a negative effect on the photosensitive material because it has a slippery polyethylene surface). That contain no substance). 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
7-6754, JP-A-58-132555, and JP-A-61-189936. When the silver halide photographic light-sensitive material of the present invention is packaged in these packaging bags, it may be packaged under reduced pressure to reduce the air in the packaging bags. Here, the absolute humidity is defined as the number of grams of water vapor in 1 m ³ of air.

The heat treatment of the present invention needs to be performed at a temperature of 30 ° C. or higher, but can be performed preferably at a temperature of 35 ° C. to 50 ° C., more preferably at a temperature of 35 ° C. to 45 ° C. Although the time of the heat treatment cannot be unequivocally determined depending on the temperature, for example, at 45 ° C., about 6 hours or more is preferable. The heat treatment of the present invention, after coating and drying the silver halide photographic material,
It can be applied at any time. In general, a silver halide photographic light-sensitive material is manufactured through a process of coating and drying, winding it once into a roll, then cutting it into a predetermined size and packaging it. Therefore, when the silver halide photographic light-sensitive material is stored at an absolute humidity of 12 g / m ³ or less, for example, the heat treatment of the present invention may be carried out at the time of coating, drying, winding into a roll, cutting, or packaging. It can be applied at any time, such as when it has been done. Humidity during heat treatment is 12g
/ M ³ or less, more preferably 10 g / m ³ or less.

The polyester used for the support of the present invention is a polyester containing an aromatic secondary acid and glycol as main constituents, and polyethylene terephthalate is most convenient from the viewpoint of availability. The thickness of the polyester is not particularly limited, but is about 12 μ to 500 μ.
About 40 μm, preferably about 40 μm to 200 μm, is advantageous from the viewpoint of ease of handling and versatility. In particular, those biaxially stretched and crystallized are advantageous in terms of stability, strength and the like. The polyester support of the present invention may be provided with an undercoat layer containing gelatin, a styrene-butadiene copolymer, vinylidene chloride, an aqueous polyester, an aqueous polyurethane or the like, if necessary, before coating the hydrocolloid layer. . In particular, an undercoat layer containing vinylidene chloride is preferably used,
In combination with the present invention, a remarkable dimensional stability improving effect is exhibited.
Further, in the present invention, the surface of the polyester support may be subjected to a surface treatment such as a corona treatment or a glow discharge treatment before applying the undercoat layer.

Next, the structure of the silver halide light-sensitive material of the present invention on the side of the silver halide emulsion layer will be described. The silver halide light-sensitive material of the present invention may have one silver halide emulsion layer,
Two or more layers may be used. The silver halide emulsion of the photographic material used in the present invention is usually a water-soluble silver salt (for example, silver nitrate).
It is prepared by mixing a solution and a water-soluble halogen salt (eg, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. 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 grains may be tabular grains having an aspect ratio of 3 or more, potato-like grains, cubes, octahedrons and the like. In addition to the silver halide emulsion layer, it may have a surface protective layer, an intermediate layer, an antihalation layer and the like, and the surface protective layer may be two or more layers.

There are no particular restrictions on the various additives and development processing methods used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item Applicable part 1) Silver halide emulsion and its production method JP-A-2-97937, page 20, lower right column, 1 production method From line 2 to page 21, lower left column, line 14 and JP-A-2-12236, No. 7 From line 19 in the upper right column of the page to line 12 in the lower left column of the same page 8. 2) Spectral sensitizing dye: JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8; 3) Surfactant / Antistatic agent JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 18, lower right column, 18th line. 4) Antifoggants / stabilizers JP-A-2-103526, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5 5) Polymer latex, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group, page 18, lower right column, line 6 to page 19, lower left column, line 1 and JP-A-2-55349, page 8, lower right column, line 13 to page 11, upper left Column 8 line. 7) Polyhydroxybenzenes, page 11, line 9 from the upper left column to line 17 from the lower right column. 8) Matting agent, slip agent, plasticizer JP-A-2-103526, page 19, upper left column, line 15 to page 19, upper right column, line 15; 9) Hardener JP-A-2-103536, page 18, upper right column, 5th line to 17th line. 10) Dyes, page 17, lower right column, lines 1 to 18 11) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 12) Developing Solution and Developing Method JP-A-2-55349, page 13, lower right column, line 1 to page 16, upper left column, line 10. The present invention can be applied to silver halide photographic materials such as printing materials, microfilm materials, medical X-ray materials, industrial X-ray materials, general negative materials, and general reversal materials. Can be. Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[0028]

【Example】

Example 1 A back layer having the following formulation was applied to one side of a 100 μm-thick biaxially stretched polyethylene terephthalate support having an undercoat layer on both sides in the order from the support and dried, and then a polymer layer was formed using a wire bar. Coated and dried.

(1) Back layer formulation Gelatin The coating amount is as shown in Table 1. Ethyl acrylate latex (average particle size: 0.1 μ) 500 mg / m ² 1,3-divinylsulfonyl-2-propanol Polystyrene sulfonate sodium salt 55 mg / m ² polymethyl methacrylate particle diameter (average particle size 3.mu.) 40 mg / m ² drying 40 ° C. 5 min (2) as C ₈ F ₁₇ of the polymer layer formulation binder (kind table as -1) coating amount Table 1 SO ₃ K 5 mg / m ² B-1 Methyl methacrylate: 2-methylhexyl acrylate: styrene: methacrylic acid = 50: 35: 1
3: 2 latex B-2 methyl methacrylate: butyl methacrylate: styrene: methacrylic acid = 35: 50: 14: 1 latex B-3 methyl methacrylate: ethyl acrylate:
Styrene: acrylic acid = 60: 30: 9: 1 latex drying 50 ° C for 5 minutes

Then, a silver halide emulsion layer 1, a silver halide emulsion layer 2, a protective layer 1, and a protective layer 2 were coated in this order from the support near the opposite surface. (3) The silver halide emulsion layer 1 Formulation I solution; water 300 ml, gelatin 9 g II solution; Agno ₃ 100 g, water 400 ml III A _{solution; NaCl37g, (NH 4) 3} RhCl
₆ 1.1 mg, water 400 ml To solution I kept at 45 ° C., solution II and solution IIIA were simultaneously added at a constant rate. After removing soluble salts from this emulsion by a conventional method well known in the art, gelatin was added and 6-methyl-4-hydroxy-1,3,3a, 7- was used as a stabilizer.
Tetrazaindene was added. This emulsion was a monodisperse emulsion having an average grain size of 0.20 μm, and the amount of gelatin contained per kg of the emulsion was 60 g. The following compounds were added to Emulsion A thus obtained. Compound a 5 × 10 ^-3 mol / Ag 1 mol Compound b 120 mg / m ² Compound c 20 mg / m ² Compound d 20 mg / m ² Compound e 9 mg / m ²

[0031]

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Polyethylenesulfonic acid sodium salt 30 mg / m ² N-oleoyl-N-methyltaurine sodium salt 50 mg / m ² 1,2-bis (vinylsulfonylacetamido) ethane 70 mg / m ² 1-phenyl-5-mercapto Tetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.1 μ) 40 mg / m ^{2 The} coating solution thus obtained was coated with an amount of gelatin of 0.75 g /
m ² , and the coated silver amount was 0.75 g / m ² .

(4) Silver halide emulsion layer 2 formulation I solution; 300 ml of water, 9 g of gelatin II solution; 100 g of AgNo ₃ , 400 ml of water III solution B: 37 g of NaCl, (NH ₃ ) RhCl ₆
Emulsion B was prepared in the same manner as Emulsion A, except that Solution IIIA was used instead of Solution IIIA. This emulsion had an average grain size of 0.2
It was a 0 μ monodisperse emulsion. The following compounds a) to emulsion B thus obtained which were used in the preparation of emulsion A)
E) and other compounds were added. Compound-A 5 × 10 ^-3 mol / Ag 1 mol Compound-B 120 mg / m ² 〃-C 100 mg / m ² 〃-D 100 mg / m ² 〃-E 9 mg / m ² Polystyrene sulfonic acid sodium salt 50 mg / m ² N -Oleoyl-N-methyltaurine sodium salt 40 mg / m ² 1,2-bis (vinylsulfonylacetamide) ethane 85 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0 0.1 μ) 40 mg / m ^{2 The} coating solution thus obtained was coated with a gelatin coating amount of 0.75 g / m ^2.
m ² and the applied silver amount was 0.6 g / m ² .

(5) Formulation of protective layer 1 Gelatin 0.9 g / m ² Lipoic acid 5 mg / m ² Dodecylbenzenesulfonic acid sodium salt 5 mg / m ² Compound-c 20 mg / m ² Poly (degree of polymerization 5) oxyethylene nonylphenol ether Sodium sulfate 5 mg / m ² sodium polystyrene sulfonate 10 mg / m ² Compound-F 20 mg / m ²

[0035]

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Ethyl acrylate latex (average particle size 0.1 μm) 200 mg / m ² (6) protective layer 2 formulation Gelatin 0.6 g / m ² polymethyl methacrylate fine particles (average particle size 3 μm) 60 mg / m ² dodecylbenzenesulfonic acid Sodium salt 20 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3 mg / m ² poly (degree of polymerization 5) oxyethylene nonyl phenol ether sulfate sodium salt 15 mg / m ² polystyrene sulfonate sodium salt 2mg / m ²

The sample thus obtained was subjected to a heating at 25 ° C. and 60%
After storage for 2 weeks in an atmosphere of RH, the following evaluation was performed. The results are shown in Table 1. (Moisture Permeability Coefficient) The coating solution for the polymer layer was flowed on a Teflon sheet and dried at 50 ° C. and 60% RH for 5 minutes to obtain a 100 μm thick film. This film is dried with calcium chloride 15
g in a moisture-permeable cup (manufactured by Toyo Seiki Co., Ltd.), placed in an atmosphere of 25 ° C. and 85% RH for 16 hours, weighed, and defined as W ₁ . Further measured again weight after placing 4 hours which is referred to as W _2. From the above results, the moisture permeability coefficient was determined by the following equation. Permeance _{= {(W 2 -W 1)} × 0.01} / {(3 2 × π) × (4 × 60 × 60) × 2.06} where 0.01 is the thickness of the film (cm), 3 ² × π is the area of the film (cm ² ), 4 × 60 × 60 is the measurement time (sec)
, 2.06 represent the water vapor pressure difference (cmHg) on both sides of the film.

(Curl) A sample cut to a length of 5 cm and a width of 1 cm was conditioned at 25 ° C. and 60% RH for 3 days.
After moving to an atmosphere of% RH, the curl value was measured 1 minute and 2 hours later. However, the curl value was defined by the following equation. Curl value = 1 / (radius of curvature of sample (cm)) However, the curl value is a positive value when the emulsion surface is on the inside and a negative value when the emulsion surface is on the outside.
The range is 2 to +0.02.

(Drying Time of Automatic Developing Machine) A sample having a size of 4 pieces is developed with an FG460A automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) in an atmosphere of 25 ° C. and 60% RH. At this time, the processing time is increased from 20 seconds to 5 seconds by changing the line speed of the automatic developing machine. The degree of drying of the sample immediately after the development processing is classified into the following three levels.
Of these levels, the practically acceptable level is the O level. Table 1 shows the shortest processing time to reach the レ ベ ル level. ：: Completely dry. The film is warm △: Slightly creased. Film temperature is about room temperature ×: Not dried. The films adhere to each other. The developing conditions are as follows. Development GR-D1 (Fuji Photo Film Co., Ltd.) Fixing GR-F1 (１) Dryer 45 ° C.

[0040]

[Table 1]

Example 2 A 180 μm thick polyethylene terephthalate support having an undercoat layer coated on both sides was coated on one side with a back layer having the following formulation in the order of distance from the support, dried and then polymer layer was dried. . However, the application of the polymer layer was performed by a wire bar method. (1) Prescription of back layer Gelatin The coating amount is as shown in Table 2. Polymethyl methacrylate fine particles (average particle size: 3 μ) 50 mg / m ² Sodium dodecylbenzenesulfonate 10 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² N, N ′ -Ethylene bis- (vinylsulfoacetamide) 1% of gelatin coating amount Ethyl acrylate latex (average particle size 0.1 μ) 1.0 g / m ²

(2) Formulation of polymer layer Binder (type is as shown in Table 2) Coating amount is as shown in Table 2 Polymethyl methacrylate fine particles (average particle size 3 μ) 10 mg / m ² C ₃ F ₁₇ SO ₃ K 5 mg / m ² (distilled water is used as the solvent for the coating solution) Drying is 180 ° C for 3 minutes

(2 ′) Formulation of polymer layer (sample 109) Gelatin The coating amount is as shown in Table 1. Sodium dodecylbenzenesulfonate 15 mg / m ² N, N′-ethylenebis- (vinylsulfoacetamide) 1 weight of gelatin % Polymethyl methacrylate fine particles (average particle size: 3 μm) 10 mg / m ² C ₈ F ₁₇ SO ₃ K 5 mg / m ²

Then, an emulsion layer and a surface protective layer were coated on the opposite side of the support in the order from the support. (3) Formulation of emulsion layer (Preparation of silver halide emulsion) 40 g of gelatin was dissolved in 1 liter of H ₂ O, and 6 g of sodium chloride, 0.4 g of potassium bromide, and compound

[0045]

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After adding 60 mg of the solution, 600 ml of an aqueous solution containing 100 g of silver nitrate and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride are added by a double jet method to form a core portion of 20 mol% of silver chloride. ,
Thereafter, 500 ml of an aqueous solution containing 100 g of silver nitrate and 500 ml of an aqueous solution containing 40 g of potassium bromide, 14 g of sodium chloride, and potassium hexachloroiridate (III) (10.7 mol / mol silver) were added by a double jet method. Forming a shell part of 40 mol% of silver chloride;
So-called core / shell cubic monodispersed silver chlorobromide grains having an average grain size of 0.35 µm were prepared. After desalting this emulsion, 40 g of gelatin was added, and the pH was 6.0 and the pAg was
8.5 to match triethylthiourea 2mg and chloroauric acid 4
mg and 4-hydroxy-6-methyl-1,3,3a,
0.2 g of 7-tetrazaindene was added and chemically sensitized at 60 ° C (emulsion A).

(Preparation of Emulsion Coating Solution) A container in which 850 g of Emulsion A was weighed was heated to 40 ° C., and additives were added by the following method to prepare an emulsion coating solution. (Emulsion coating liquid formulation A) Emulsion A 850 g Compound (h) 1.2 × 10 ^-4 mol Compound (li) 0.8 × 10 ^-3 mol Compound (nu) 1 × 10 ^-3 mol Polyacrylamide (molecular weight 40,000) 7.5 g Trimethylol propane 1.6 g Na polystyrene sulfonate 2.4 g Latex of poly (ethyl acrylate / methacrylic acid) 16 g N, N'-ethylenebis- (vinylsulfone acetamide) 1.2 g This coating solution is coated with gelatin. The amount of silver applied was 1.5 g / m ² , and the amount of silver applied was 2.5 g / m ² .

[0048]

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(4) Preparation of Surface Protective Layer (Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer) A container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution. (Formulation of coating solution for surface protective layer of emulsion layer) Gelatin 100 g Polyacrylamide (molecular weight 40,000) 10 g Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g N, N'-ethylenebis- (vinylsulfone acetamide) 1.5 g Poly Methyl methacrylate fine particles (average particle size: 2.0 μm) 2.2 g Sodium t-octylhexyethoxyethoxyethanesulfonate 1.2 g C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 2.7 g sodium polyacrylate _{4g C 8 H 17 SO 3 K} 70mg C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg NaOH (1N) 4ml methanol 60 ml This coating solution was applied so that the amount of gelatin applied was 1 g / m ² .

The sample thus obtained was heated at 25 ° C. and 60%
The same evaluation as in Example 1 was performed under the RH atmosphere for 2 weeks. However, the automatic developing machine drying time was evaluated under the following conditions. Automatic developing machine NRN automatic processing machine (manufactured by Fuji Photo Film Co., Ltd.) Developing RD-10 (〃) Fixing RF-10 dryer 55 ° C. The results are shown in Table-2.

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[Table 2]

Example 3 A back layer having the following formulation was applied to one surface of a biaxially stretched polyester support having a thickness of 100 μm provided with an undercoat layer.
Dry at 0 ° C. for 5 minutes. Next, a polymer layer was applied thereon and dried at 180 ° C. for 3 minutes.

(1) Formulation of back layer Gelatin 3.0 g / m ² 1,3-divinylsulfonyl-2-propanol 150 mg / m ² Polystyrene sulfonate sodium salt 40 mg / m ²

(2) Formulation of polymer layer Binder Type is as shown in Table-3. 1 g / m ² B-1 Methyl methacrylate: styrene: 2-ethylhexyl acrylate: methacrylic acid = latex of B: 60: 15: 24: 1 B-2 ethylene : Acrylic acid = 98: 2 latex Polymethyl methacrylate fine particles (average particle size 3.5) 8 mg / m ²

Then, a silver halide emulsion layer 1, a silver halide emulsion layer 2, a protective layer 1 and a protective layer 2 were simultaneously coated in this order from the support near the opposite surface, and dried under the conditions shown in Table 3.

(3) Silver halide emulsion layer 1 Formulation I solution; 300 ml of water, 9 g of gelatin II solution; 100 g of AgNO ₃ , 400 ml of water III A solution; 37 g of NaCl, (NH ₄ ) ₃ RhCl
₆ 1.1 mg, water 400 ml To solution I kept at 45 ° C., solution II and solution IIIA were simultaneously added at a constant rate. After removing soluble salts from this emulsion by a conventional method well known in the art, gelatin was added and 6-methyl-4-hydroxy-1,3,3a, 7- was used as a stabilizer.
Detrazaindene was added. This emulsion was a monodisperse emulsion having an average grain size of 0.20 μm, and the amount of gelatin contained per kg of the emulsion was 60 g. The following compounds were added to Emulsion A thus obtained. Compound a 5 × 10 ⁻³ mol / AgI mol Compound b 120 mg / m ² Compound c 20 mg / m ² Compound d 20 mg / m ² Compound e 9 mg / m ²

Polystyrenesulfonic acid sodium salt 30 mg / m ² N-oleoyl-N-methyltaurine sodium salt 50 mg / m ² 1,2-bis (vinylsulfonylacetamide) ethane 70 mg / m ² 1-phenyl-5-mercapto Tetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.1 μm) 40 mg / m ^{2 The} coating solution thus obtained was applied so that the coated silver amount was 1 g / m ² .

(4) Silver halide emulsion layer 2 formulation I solution; 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, (NH ₃ ) RhCl ₆
Emulsion B was prepared in the same manner as Emulsion A, except that Solution IIIA was used instead of Solution IIIA. This emulsion had an average grain size of 0.2
It was a 0 μ monodisperse emulsion. The following compounds (e) used in Emulsion B thus obtained were used in preparing Emulsion A)
G) and other compounds were added. Compound-A 5 × 10 ^-3 mol / Ag 1 mol Compound-B 120 mg / m ² 〃-C 100 mg / m ² 〃-D 100 mg / m ² 〃-E 9 mg / m ² Polystyrene sulfonic acid sodium salt 50 mg / m ² N -Oleoyl-N-methyltaurine sodium salt 40 mg / m ² 1,2-bis (vinylsulfonylacetamide) ethane 85 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0 0.1 μ) 40 mg / m ^{2 The} coating solution thus obtained was applied so that the coated silver amount was 0.6 g / m ² .

(5) Formulation of protective layer 1 Gelatin 0.9 g / m ² Lipoic acid 5 mg / m ² Dodecylbenzenesulfonic acid sodium salt 5 mg / m ² Compound-c 20 mg / m ² Poly (degree of polymerization 5) oxyethylene nonylphenol ether Sodium sulfate 5 mg / m ² sodium polystyrene sulfonate 10 mg / m ² Compound-F 20 mg / m ²

Ethyl acrylate latex (average particle size 0.1 μ) 200 mg / m ² (6) protective layer 2 formulation Gelatin 0.6 g / m ² polymethyl methacrylate fine particles (average particle size 3 μ) 60 mg / m ² dodecylbenzenesulfonic acid Sodium salt 20 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3 mg / m ² poly (degree of polymerization 5) oxyethylene nonyl phenol ether sulfate sodium salt 15 mg / m ² polystyrene sulfonate sodium salt 2 mg / m ² The sample thus obtained was heat-treated under the conditions shown in Table 3 and then stored for 2 weeks under the conditions shown in Table 3, and then the following evaluation was performed.

[Evaluation Method of Dimensional Change Associated with Processing] Sample 20
Drill two holes with a diameter of 8 mm at an interval of 0 mm,
After being left in a room of 0% RH, the distance between the two holes was accurately measured using a pin cage with an accuracy of 1/1000 mm. The length at this time is X mm. Then, after being developed, fixed, washed with water, and dried by an automatic developing machine, the size after 5 minutes was changed to Ymm.
And The dimensional change rate (%) due to processing is 200 for YX.
Was evaluated by multiplying the value obtained by dividing by 100 by 100. In the art, if the dimensional change rate is ± 0.01% or less, there is no practical problem, and if it is ± 0.007% or less, it is considered very preferable. The development process was performed using Fuji Photo Film FG-
460A automatic developing machine, and developer and fixer GR-
D1 and GR-F1 were used at 38 ° C. for 20 seconds. The drying temperature at that time was 45 degrees.

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[Table 3]

Continuation of front page (56) References JP-A-2-11047 (JP, A) JP-A-58-58541 (JP, A) JP-A-56-159640 (JP, A) JP-A-57-8540 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/76 502 G03C 1/04 501 G03C 1/74 G03C 1/795 G03C 1/81

Claims (3)

(57) [Claims] 1. A support having at least one silver halide emulsion layer having at least one hydrophilic colloid as a binder on one surface of the support, and the surface of the support opposite to the surface on which the silver halide emulsion layer is provided. In a silver halide photographic material having at least one non-photosensitive hydrophilic colloid layer, the total amount of the hydrophilic colloid on the surface on which the silver halide emulsion layer is coated and on the opposite surface A weight ratio of 0.3 or more, and a moisture permeability coefficient of 0.10 × 10 4 at a position on the surface on which the non-photosensitive hydrophilic colloid layer is coated, separated from the support from the non-photosensitive hydrophilic colloid layer. ^{-10 g · cm / cm 2 /} sec / cmHg
A silver halide photographic material comprising the hydrophobic polymer layer described above. 2. When a hydrophilic colloid layer coating solution is applied and dried on a polyester support by using a polyester support, 300% or less based on the dry weight of the binder contained in all the layers formed on the support. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the water is dried at a relative humidity of 50% or less, and stored in an atmosphere having an absolute humidity of 12 g / m ³ or less after drying. 3. The silver halide according to claim 2, wherein said silver halide photographic material is subjected to a heat treatment at a temperature of 30 ° C. or more in an atmosphere having an absolute humidity of 12 g / m ³ or less after drying. Photosensitive material.