JPH1048777A - Silver halide photographic sensitive material and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material and its manufacturing method improved in water resistance and prevented from opacity of coating films. SOLUTION: The silver halide photographic sensitive material has a silver halide emulsion layer on one side of a support and on its other side a nonphotosensitive hydrophilic colloidal layer and the outermost hydrophobic polymer layer, and the water resistance of this hydrophobic polymer layer is kept by inserting an interlayer using a water-soluble polymer as a binder between the hydrophilic colloidal layer and the hydrophobic polymer layer or by forming these hydrophilic colloidal layer and hydrophobic polymer layer and drying them and then preserving the photosensitive material in an atmosphere at a temperature by 20 deg.C lower than the glass transition point of the binder of the hydrophobic polymer layer, and further by controlling the pH so as to adjust the charge of the hydrophilic colloidal layer and that of the hydrophobic polymer layer to the same positive or negative side, and by setting the difference between the dry bulb temperature and the wet bulb temperature of the drying air in the drying process to >=7 deg.C.

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 method for producing a silver halide photographic light-sensitive material having suitability for rapid drying during development and preservation of a developing solution.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials have been required to have a preserving property and a rapid processability of a developing solution.

[0003] As a method for improving the preservability and rapid processing suitability of a developing solution, a non-photosensitive colloid layer is coated on the opposite surface (hereinafter referred to as "back surface") of a support having a silver halide photosensitive layer. It is effective to make it hydrophobic without providing.

However, this method cannot prevent deformation (hereinafter referred to as "curl") of a silver halide photographic material due to a change in humidity of an environment in which the material is placed.

[0005] As a method for improving the preservability of the developing solution and the suitability for rapid developing process and preventing the curl of the silver halide photographic material, a non-photosensitive hydrophilic colloid layer is formed on the back surface and a hydrophobic colloid layer is formed on the outside thereof. A method of applying a polymer layer is disclosed in Japanese Patent Application Laid-Open No. 5-232625.

Further, as a method for improving the scratch resistance of the hydrophobic polymer layer, a method of adding colloidal silica gel to the hydrophobic polymer layer (JP-A-5-232626) and a method of adding a slip agent ( JP-A-6-1904
No. 2) is disclosed.

[0007] However, the method in which the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are simultaneously applied onto a support while being superimposed achieves high productivity, but has the following problems.

That is, when the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are overlapped, the binder of the hydrophilic colloid layer diffuses into the hydrophobic polymer layer, and the water resistance of the hydrophobic polymer layer is reduced. As a result, there arises a disadvantage that the preservation property and rapid processing suitability of the developing solution cannot be obtained.

When the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are overlaid, if the charges of the hydrophilic colloid and the hydrophobic polymer have opposite signs, they are bound by electrostatic interaction. The coating is devitrified by forming aggregates. Alternatively, after applying the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer on a support, there is a disadvantage that the coating film is deformed and devitrified in a drying step.

[0010]

The first object of the present invention is to provide a method in which a non-photosensitive hydrophilic colloid layer and a hydrophobic polymer layer are simultaneously provided on the back surface of a support of a silver halide light-sensitive material while being superposed. Another object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material which ensures the water resistance of the hydrophobic polymer layer, and has the preservability of a developing solution and the suitability for rapid processing.

A second object of the present invention is to provide a method in which a non-photosensitive hydrophilic colloid layer and a hydrophobic polymer layer are simultaneously provided on a back surface of a support of a silver halide light-sensitive material while being superposed.
An object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material which does not cause devitrification of a coating film and has a preserving property of a developing solution and a suitability for rapid processing.

[0012]

SUMMARY OF THE INVENTION A first object of the present invention is to:
A silver halide emulsion layer having at least one hydrophilic colloid as a binder is coated on one surface of the support, and a hydrophilic surface is provided on the surface of the support opposite to the surface on which the silver halide emulsion layer is coated. Silver halide photograph in which a non-photosensitive hydrophilic colloid layer using a hydrophilic colloid as a binder, and a hydrophobic polymer layer composed of an aqueous dispersion of a hydrophobic polymer layer are coated on the outermost layer of the non-photosensitive hydrophilic colloid layer A photosensitive material, wherein the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are provided on a support while simultaneously layering the non-photosensitive hydrophilic colloid layer and subsequently dried; The non-photosensitive hydrophilic colloid layer and the hydrophobic polymer by inserting a layer using a water-soluble polymer as a binder in the middle of the water-soluble polymer layer, or without providing such a water-soluble polymer intermediate layer. Also achieved by storing at the 20 ° C. temperature lower than the ambient relative glass transition temperatures of hydrophobic polymers hydrophobic polymer layer after applying drying on a support.

A second object of the present invention is to provide a silver halide emulsion layer having at least one layer of a hydrophilic colloid as a binder on one surface of a support, wherein the silver halide emulsion layer of the support is provided. A non-photosensitive hydrophilic colloid layer using a hydrophilic colloid as a binder and a hydrophobic polymer layer on the outermost layer of the non-photosensitive hydrophilic colloid layer were coated on the surface opposite to the surface on which is coated. A method for producing a silver halide photographic material, wherein the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are applied on a support while simultaneously superimposing the layers, followed by drying, wherein the hydrophilic colloid layer is The pH is adjusted so that the electric charge and the electric charge of the hydrophobic polymer have the same sign, and the temperature difference between the dry-bulb temperature and the wet-bulb temperature of the drying air in the drying step is 7 ° C. or more. Silver halide It is achieved by the method for producing a true-sensitive material.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In order to realize the preservability and rapid processing suitability of a developing solution of a silver halide photosensitive material, a hydrophilic colloid layer on a support surface (back surface) on which a silver halide photosensitive layer is not coated is subjected to development processing. It is required not to swell with the liquid. Therefore, a technique has been developed to prevent the development processing solution from penetrating into the hydrophilic colloid layer by providing a hydrophobic polymer layer on the outer surface of the hydrophilic colloid layer on the back surface (Japanese Patent Laid-Open No. Hei 5-232625). However, when the hydrophilic colloid layer and the hydrophobic polymer layer on the back surface are applied simultaneously on a support to obtain high productivity (hereinafter referred to as "multilayer coating"), the following phenomenon occurs. Quality is impaired. When a hydrophilic colloid layer and a hydrophobic polymer layer composed of an aqueous dispersion of a hydrophobic polymer are overlaid, the binder of the hydrophilic colloid layer diffuses into the hydrophobic polymer layer, and the binder of the hydrophilic colloid layer becomes a water path. When the hydrophobic polymer layer is made of an aqueous dispersion of a hydrophobic polymer, the binder of the hydrophilic colloid layer adheres to the surface of the water-dispersed hydrophobic polymer particles, and the hydrophobic polymer particles fuse with each other. By inhibiting adhesion, there is a problem that the hydrophobic polymer layer does not have sufficient water resistance, and the preservability and rapid processing suitability of the developing solution cannot be obtained.

However, when a layer containing a water-soluble polymer as a binder is inserted between the hydrophilic colloid layer and the hydrophobic polymer layer, the diffusion of the binder of the hydrophilic colloid layer into the hydrophobic polymer layer is prevented. Because of the suppression, no water path is formed in the hydrophobic polymer layer, and the fusion of the hydrophobic polymer particles is not hindered. Therefore, the hydrophobic polymer exhibits sufficient water resistance.

A method for imparting water resistance to the hydrophobic polymer instead of providing the water-soluble polymer intermediate layer will be described below.

The hydrophilic colloid layer and the hydrophobic polymer layer are provided on a support, and after drying, stored at a temperature not lower than the glass transition temperature of the hydrophobic polymer, that is, 20 ° C. or higher. Then, the fusion of the hydrophobic polymer particles due to the molecular diffusion of the hydrophobic polymer gradually progresses, and the binder of the hydrophilic colloid layer diffused in the hydrophobic polymer layer is dispersed in an island shape ( (Dispersed phase) and exhibit water resistance. It is preferable that the storage temperature is higher than the glass transition temperature of the hydrophobic polymer, and the storage period required for exhibiting water resistance may be short.
The storage may be performed after the hydrophilic colloid layer and the hydrophobic polymer layer on the back surface are coated on the support, or the hydrophilic colloid layer and the hydrophobic polymer layer may be supported on the back surface. The silver halide emulsion layers may be stored on the opposite side of the body after each application.

Further, as described above regarding the problem of devitrification of the coating film, when the hydrophilic colloid layer and the hydrophobic polymer layer are overlapped, both the hydrophilic colloid which is the binder of the back layer and the binder of the polymer layer have a dissociation group. When the film is ionic, the hydrophilic colloid molecules and the polymer layer binder molecules may aggregate to devitrify the coating film. In order to avoid aggregation, it is necessary to adjust the pH so that the sign of the charge of the hydrophilic colloid molecule and the sign of the charge of the polymer layer binder molecule are the same. For example, the binder of the polymer layer is an aqueous dispersion of a polymer containing an acid component such as methacrylic acid, which is adjusted to a high pH to enhance dispersibility, the acid component dissociates, and the polymer has a negative charge. In the case where an aqueous gelatin solution is used as the hydrophilic colloid of the back layer, the pH of the aqueous gelatin solution of the back layer needs to be set higher than the isoelectric point.

After the hydrophilic colloid layer and the hydrophobic polymer layer of the back layer are provided on the support and then gradually dried, the hydrophobic polymer layer of the outer layer is first dried to form a film, and then the hydrophilic layer is formed. When the colloid layer shrinks during drying, the hydrophobic polymer layer may be buckled by the force of shrinkage of the hydrophilic colloid layer, deformed, and devitrified. To prevent the occurrence of devitrification, it is necessary to dry the hydrophilic colloid layer at about the same time as the hydrophobic polymer layer dries and forms a film. That is, it is preferable that the temperature difference between the dry-bulb temperature and the wet-bulb temperature that determines the drying speed is 7 ° C. or more.

The back layer of the present invention is a layer using a hydrophilic colloid as a binder. The hydrophilic colloid used is a binder for a photographic layer on the side on which a silver halide emulsion layer is coated from the viewpoint of curling. Those having a moisture absorption rate and a moisture absorption rate close to the above are preferred, and gelatin is the most preferred.

As the gelatin, any of those generally used in the art such as lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, and modified gelatin can be used. As hydrophilic colloids other than gelatin, colloidal albumin, proteins such as casein, agar, sodium alginate, sugar derivatives such as starch derivatives, carboxymethylcellulose, hydroxymethylcellulose compounds, polyvinyl alcohol, poly-
Synthetic hydrophilic compounds such as N-vinylpyrrolidone and polyacrylamide can be used.

In the back layer of the present invention, in addition to a binder, a photographic additive such as an inorganic fine particle such as a matting agent, a surfactant, a crosslinking agent, a thickener, a preservative, an ultraviolet absorber, and colloidal silica is added. You may. A polymer latex may be further added to the back layer. The polymer latex is an aqueous dispersion of a water-insoluble polymer having an average particle diameter of 20 μm to 200 μm, and is preferably used in an amount of 0.01 to 1.0 part by weight, particularly preferably 0.1 to 1.0 part by weight, based on 1 part by weight of the binder.
0.8 parts by weight. 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 100,000. Above, particularly preferably 300,000 to 500,000 polymers.

The back layer of the present invention may be a single layer or two or more layers. The thickness of the back layer is not particularly limited, and it depends on the type of the photographic material to be applied. From the viewpoint of curling, it is desirable that the thickness corresponds to or close to the thickness of the photosensitive silver halide emulsion layer side. About 0.2 μm to 20 μm, especially 0.5 μm to 10 μm
m is preferred. When the back layer comprises two or more layers, the sum of the thicknesses of all the back layers is defined as the thickness of the back layer of the silver halide photographic light-sensitive material of the present invention.

The back layer of the present invention is desirably substantially water-resistant by being provided with a hydrophobic polymer layer. The dispersion medium of the coating liquid for the hydrophobic polymer layer may usually be water, and the concentration of the hydrophobic polymer is about 1 to 50% by weight, preferably about 5 to 30% by weight. “Substantially water-resistant” means that the thickness of the back layer after immersion in water at 25 ° C. for 1 minute is 1.5 times or less the thickness of the back layer before immersion, and 1.3 times or less. It is preferable that

Next, the hydrophobic polymer layer of the present invention (hereinafter referred to as "polymer layer") will be described. The polymer layers of the present invention are substantially water resistant. “Substantially water-resistant” means that the thickness of the polymer layer after immersion in water at 25 ° C. for 1 minute is not more than 1.2 times the thickness of the polymer layer before immersion, and preferably 1.1 times. Less than twice.

In the present invention, when the back layer and the hydrophobic polymer layer are laminated, “substantially water-resistant” means that the film is immersed in water at 25 ° C. for 1 minute with respect to the total thickness of the back layer and the hydrophobic polymer layer. The total thickness after immersion is 1.
5 times or less, preferably 1.3 times or less,
The increase in thickness (swelling thickness) after immersion in water is 2 μm or less, and preferably 1 μm or less. Actually, the swelling thickness at the end of the development processing step is 2 μm or less, preferably 1 μm or less. The conditions of the development processing step vary depending on the type of the photosensitive material, the processing system and the like. If the water resistance is not obtained, the swelling thickness during processing cannot be kept small.

The binder of the polymer layer of the present invention is not particularly limited as long as the polymer layer and the back layer become “substantially water-resistant”. Specific examples of the polymer layer binder include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, epoxy resin, fluorine resin such as polyvinylidene fluoride, butadiene rubber, chloroprene rubber, and natural rubber. Examples include rubbers such as rubber, water-insoluble polymers such as acrylic acid or methacrylic acid esters such as polymethyl methacrylate and polyethyl acrylate, 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 optionally contain a photographic additive such as a matting agent, a surfactant, a crosslinking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica. Good.

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, there is a preferable range for the thickness of the polymer layer. In other words, when the thickness of the polymer layer is smaller than the preferred range, the water resistance of the polymer layer becomes insufficient, the back layer swells in the treatment liquid, and when the thickness of the polymer layer is larger than the preferred range, the water vapor of the polymer layer becomes larger. Insufficiency in permeability causes inhibition of moisture absorption and desorption of the hydrophilic colloid layer of the back layer, which is not balanced with the amount of expansion and contraction of the silver halide emulsion layer, resulting in a disadvantage that curling becomes poor. The preferred thickness of the polymer layer is in the range of 0.05 to 10 μm, more preferably 0.1 to 5 μm, depending on the type of binder in the polymer layer. 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 polymer layer thickness of the silver halide photographic material of the present invention.

In the present invention, for the purpose of imparting water resistance to the hydrophobic polymer, the water-soluble polymer for the intermediate layer provided between the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer may be polyvinyl alcohol, Polyacrylamide, polyethylene glycol, water-soluble polyester, water-soluble nylon, water-soluble acrylic acid or methacrylic acid ester polymer, water-soluble synthetic polymers such as polyvinylamine derivatives, polyvinylpyrrolidone, cellulose derivatives such as hydroxyethylcellulose and carboxymethylcellulose, starch derivatives, etc. Natural or semi-synthetic polymers can be used.

The molecular weight of the water-soluble polymer used as a binder in the intermediate layer of the present invention must be large in order to form a diffusion barrier, and is suitably 300,000 or more. On the other hand, the upper limit of the molecular weight is not limited as long as it can exhibit water solubility.
It is preferably 1,000,000 or less, more preferably 500,000 or less. The thickness of the intermediate layer is 2 μm because the increase in the drying load does not cause a decrease in the production rate.
Hereinafter, the thickness is preferably about 0.02 to 1 μm, and more preferably about 0.1 to 0.5 μm.

In the intermediate layer of the present invention, in addition to the water-soluble polymer as a binder, an adsorbent such as colloidal silica for trapping hydrophilic colloid molecules diffused from the hydrophilic colloid layer, and a hydrophilic colloid molecule May be added, and a crosslinking agent such as a metal ion may be added to quickly cross-link and further suppress diffusion into the hydrophobic polymer layer.

The dispersion medium of the intermediate layer coating solution is usually water,
The concentration of the water-soluble polymer is about 1 to 20% by weight, preferably about 2 to 10% by weight.

The viscosities of the back layer, the intermediate layer and the polymer layer of the present invention are not particularly limited, but when the viscosity of the intermediate layer or the polymer layer is extremely high or extremely low compared to the viscosity of the back layer, If two layers of the back layer and the polymer layer or the three layers of the back layer, the intermediate layer and the polymer layer overlap and flow, the flow becomes unstable, causing ripples and uneven thickness of the coating film. Therefore, the viscosity ratio of the intermediate layer and the polymer layer to the back layer is preferably 0.1.
It is more preferably 0.1 to 10 within the range of 01 to 100.

The support in the present invention includes a plastic film, resin coated paper and the like.
The material of the plastic film is, for example, polyethylene, polyolefin such as polypropylene, polyvinyl acetate, polyvinyl chloride, vinyl polymer such as polystyrene, 6,6-nylon, polyamide such as 6-nylon,
Polyester such as polyethylene terephthalate, polyethylene naphthalate, polyethylene-2,6-naphthalate, polycarbonate, cellulose triacetate,
Cellulose acetate such as cellulose diacetate is used. An undercoat layer, such as gelatin, is optionally applied to the support surface. The resin used for coating the resin coated paper is typically a polyolefin such as polyethylene, but is not necessarily limited thereto. The surface of the resin-coated paper is not limited to a smooth surface, but may be a rough surface having irregularities if the average surface roughness is 5 μm or less.

As described above, the pH of the coating solution for the hydrophobic polymer layer and the pH of the coating solution for the hydrophilic colloid layer are adjusted so that the charges of the hydrophobic polymer particles and the hydrophilic colloid particles have the same sign. This pH can be set from each isoelectric point of the hydrophobic polymer and the hydrophilic colloid. When the isoelectric point is unknown, it can be measured by a known method. For example, a method of measuring by passing an aqueous dispersion through an ion exchange membrane can be used.

The method for applying the back layer and the polymer layer of the present invention includes slide coating, extrusion,
A system in which a plurality of layers of a coating solution such as a curtain coat are formed in a film or bead form and continuously supplied onto a support can be used.

In order to prevent devitrification, the difference between the dry-bulb temperature of the dry air and the wet-bulb temperature is preferably 7 ° C. or more, more preferably 15 ° C. or more. This temperature difference can be achieved, for example, by adjusting the relative temperature by increasing the moisture of the drying air. The temperature of the drying air is about 20 to 50 ° C., preferably 2
The drying time is about 0.5 to 10 minutes, preferably about 1 to 5 minutes.

After the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are applied to the support and dried, the temperature is not lower than the glass transition temperature of the hydrophobic polymer of the hydrophobic polymer layer by 20 ° C. or more, preferably lower by 10 ° C. or more. The water resistance of the hydrophobic polymer layer can be improved by storing at a temperature that is not higher, more preferably at or above the glass transition temperature. The upper limit of the storage temperature is a temperature at which the photographic light-sensitive material does not cause thermal fog, and is usually 50 ° C or lower, preferably 40 ° C or lower. These storage conditions are particularly effective when a layer using a water-soluble polymer as a binder is not provided.

[0041]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to this.

Example 1 A 100 μm thick polyethylene terephthalate having a gelatin undercoat layer on both surfaces was used as a support. One surface of the support was coated by slide coating with a back layer having the following formulation as a lower layer and a polymer layer as an upper layer. As the application condition by slide coating, the distance from the tip of the liquid injector to the support was 0.25 m.
m, the transport speed of the support was 150 m / min.

<Formation of Back Layer> Gelatin 2.5 g / m ² Sodium dodecylbenzenesulfonate 10 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² N, N′-ethylenebis- (vinylsulfone acetamide) 25 mg / m ²

The pH of the back layer was adjusted to 5.7 with 1N hydrochloric acid. PH of isoelectric point of gelatin used4.
It was 8. The temperature of the back layer coating solution is 35 ° C., and the viscosity at a shear rate of 10 (l / sec) is 50 to 60 mPa.
-It was s.

<Formulation of Polymer Layer> Methyl methacrylate: ethyl acrylate: glycidyl methacrylate: methacrylic acid = latex of 60: 32: 6: 2 2.0 g / m ² sodium dodecylbenzenesulfonate 16.5 mg / m ² Fine particles of polymethyl methacrylate 10 mg / m ² C ₈ F ₁₇ SO ₃ K 5 mg / m ²

<Formation of Intermediate Layer> Polyvinyl alcohol having a molecular weight of about 75,000, 150,000, or 350,000 (brand name: Kuraray Povar) and a degree of saponification of about 88% was used as a binder. Polyvinyl alcohol 200 mg / m ² Sodium dodecylbenzenesulfonate 3 mg / m ²

The pH of the intermediate layer was adjusted to 9 which is almost the same as that of the polymer layer, using 1N caustic soda.

At a humidity of 20 ° C. and a shear rate of 10 (l / sec), the molecular weight of polyvinyl alcohol is 75,000,
The viscosities of the intermediate layers of 150,000 and 350,000 were 20, 33, and 52 mPa · s, respectively.

The temperature of the coating solution for the polymer layer is 20 ° C., the viscosity at a shear rate of 10 (l / sec) is 15 mPa · s (the volume concentration of the polymer particles in the coating solution is 20%), and methacrylic acid is added to the polymer composition. % And the pH was 8.8.
The glass transition temperature of the hydrophobic polymer was 44 ° C.

On the support, three layers of a hydrophilic colloid layer, an intermediate layer and a hydrophobic polymer layer were applied. In addition, two layers of a hydrophilic colloid layer and a hydrophobic polymer layer were applied without inserting an intermediate layer (for comparison).

After coating, the coating film was gelled by blowing air having a dry bulb temperature of 20 ° C. and a wet bulb temperature of 15 ° C. in a chilling zone, and then the dry bulb temperature was 35 ° C. and the wet bulb temperature was 20 ° C.
Drying air at 0 ° C. was blown to dry. Further, a dye layer, an emulsion layer, a protective layer lower layer and a protective layer upper layer described in Example 3 of JP-A-5-127282 were simultaneously coated on the opposite surface of the support by slide coating in the order of distance from the support.
The application, chilling and drying conditions were the same as for the back and polymer layers.

Several samples were prepared by continuously applying a coating film over a length of 200 m on a support and winding the rolls into a roll. The samples were stored in an atmosphere at a temperature of 46 ° C. for 4 days and then immersed in water. Of the back layer was measured. Then, it was determined that a sample in which the increase in the thickness of the back layer and the polymer layer was 1 μm or less exhibited water resistance. Table 1 shows the results.

[0053]

[Table 1]

Example 2 A 100 μm-thick polyethylene terephthalate having a gelatin undercoat layer on both sides was used as a support. One surface of the support was coated by slide coating with a back layer having the following formulation as a lower layer and a polymer layer as an upper layer. As the application condition by slide coating, the distance from the tip of the liquid injector to the support was 0.25 m.
m, the transport speed of the support was 150 m / min.

<Prescription of Back Layer> Gelatin 2.5 g / m ² Sodium dodecylbenzenesulfonate 10 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² N, N′-ethylenebis- (vinylsulfone acetamide) 25 mg / m ²

The pH of the back layer was adjusted to 5.7 with 1N hydrochloric acid. The gelatin used had an isoelectric point pH of 4.8. The temperature of the back layer coating solution is 35
At a shear rate of 10 (l / sec) at a temperature of 50-60.
mPa · s.

<Formulation of Polymer Layer> Methyl methacrylate: ethyl acrylate: glycidyl methacrylate: methacrylic acid = latex of 60: 32: 6: 2 2.0 g / m ² sodium dodecylbenzenesulfonate 16.5 mg / m ² Polymethyl methacrylate fine particles 10 mg / m ² C ₈ F ₁₇ SO ₃ K 5 mg / m ²

The viscosity of the polymer layer coating solution at a temperature of 20 ° C. and a shear rate of 10 (l / sec) is 15 mPa · s (the volume concentration of the polymer particles in the coating solution is 20%). PH was 8.8. The glass transition temperature of the hydrophobic polymer was 44 ° C.
After the application, the dry-bulb temperature is set to 20 in the chilling zone.
After the coating film was gelled by blowing air at 15 ° C. and a wet bulb temperature of 15 ° C., it was dried by blowing dry air having a dry bulb temperature of 35 ° C. and a wet bulb temperature of 20 ° C. In addition, on the opposite side of the support,
The dye layer, the emulsion layer, the protective layer lower layer and the protective layer upper layer described in Example 3 were simultaneously coated by slide coating in the order of distance from the support. The application, chilling and drying conditions were the same as for the back and polymer layers.

A number of samples were prepared by continuously applying a coating film over a length of 200 m on a support and winding up in a roll shape, storing the samples in different temperature atmospheres, and immersing them in water for the number of storage days. The thickness of the back layer at that time was measured. Then, when the amount of increase in the thickness of the back layer became 1 μm or less, it was determined that water resistance had developed, and the number of storage days was determined. Table 2 shows the results.

[0060]

[Table 2]

From the results shown in Table 2, it can be understood that when stored at a temperature not lower than 20 ° C. below the glass transition temperature (44 ° C.) of the hydrophobic polymer, a good water resistance effect is exhibited.

Example 3 A 100 μm thick polyethylene terephthalate having a gelatin undercoat layer on both sides was used as a support. One surface of the support was coated by slide coating with a back layer having the following formulation as a lower layer and a polymer layer as an upper layer. As the application condition by slide coating, the distance from the tip of the liquid injector to the support was 0.25 m.
m, the transport speed of the support was 150 m / min.

<Prescription of Back Layer> Gelatin 2.5 g / m ² Sodium dodecylbenzenesulfonate 10 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² N, N′-ethylenebis- (vinylsulfone acetamide) 25 mg / m ²

The pH of the back layer was adjusted to 4.6, 5.7, and 6.8 by 1N hydrochloric acid or caustic soda.
The gelatin used had an isoelectric point pH of 4.8. The temperature of the back layer coating liquid was 35 ° C., and the shear rate was 10 (l).
/ Sec) was 50 to 60 mPa · s.

<Polymer Layer Formulation> Methyl methacrylate: styrene: 2-ethylhexyl acrylate = 60: 10: 30 latex 2.0 g / m ² Sodium dodecylbenzenesulfonate 16.5 mg / m ² Polymethyl methacrylate fine particles 10 mg / m ² C ₈ F ₁₇ SO ₃ K 5 mg / m ²

The temperature of the coating solution for the polymer layer was 20 ° C., the viscosity at a shear rate of 10 (l / sec) was 11 mPa · s (the volume concentration of the polymer particles in the coating solution was 20%), and acrylic acid was added to the polymer composition at 0.1%. It contained 1% and the pH was 9.8.
Therefore, in the case of the back layer having a pH of 5.7 and 6.8, the charge of the gelatin of the binder becomes negative, as in the sign of the charge of the polymer particles of the polymer layer.

After coating, the coating film was gelled by blowing air at a dry bulb temperature of 20 ° C. and a wet bulb temperature of 15 ° C. in a chilling zone, and then dried under several conditions.

Further, on the opposite surface of the support, Japanese Patent Application Laid-Open
No. 27282 The dye layer, emulsion layer, protective layer lower layer, and protective layer upper layer described in Example 3 were simultaneously coated by slide coating in the order of distance from the support.

After the application, air was blown in a chilling zone at a dry-bulb temperature of 20 ° C. and a wet-bulb temperature of 15 ° C. to gel the coating film, and then the dry-bulb temperature was 35 ° C. and the wet-bulb temperature was 2
Dry air at 0 ° C. was blown for 150 seconds. The opacity (absorbance of white light) of the obtained sample was evaluated. The tolerance for white light absorbance is 2%. Table 3 shows the results.

[0070]

[Table 3]

As can be seen from Table 3, the white light absorbance of this example is smaller than the allowable value, and the transparency is good.

[0072]

As described above, according to the present invention, a non-photosensitive hydrophilic colloid layer and a hydrophobic polymer layer are simultaneously provided on the back surface of a support on which a silver halide emulsion layer is coated. In such a case, the water resistance of the hydrophobic polymer layer is maintained, the devitrification of the coating film can be suppressed, and the production of a silver halide photographic light-sensitive material having a preservation property of a developer and a suitability for rapid processing can be achieved. The place that contributes is great.

Claims (8)

[Claims] 1. A support comprising: a support; a silver halide emulsion layer provided on at least one surface of which is provided with a hydrophilic colloid as a binder; and a hydrophilic colloid provided on the opposite surface of the support. A silver halide photographic light-sensitive material provided with a non-photosensitive hydrophilic colloid layer as a binder, and a hydrophobic polymer layer comprising an aqueous dispersion of a hydrophobic polymer provided on the outermost layer of the non-photosensitive hydrophilic colloid layer The silver halide photographic light-sensitive material according to claim 1, wherein a layer containing a water-soluble polymer having a molecular weight of 300,000 or more as a binder is provided between the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer. 2. A support having at least one silver halide emulsion layer having a hydrophilic colloid as a binder provided on one surface thereof, opposite to the surface of the support on which the silver halide emulsion layer is provided. On the side surface, a non-photosensitive hydrophilic colloid layer using a hydrophilic colloid as a binder, and a hydrophobic polymer layer composed of an aqueous dispersion of a hydrophobic polymer were coated on the outermost layer of the non-photosensitive hydrophilic colloid layer. A method for producing a silver halide photographic material, wherein the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are provided on a support while simultaneously layering the non-photosensitive hydrophilic colloid layer, and subsequently dried. A method for producing a silver halide photographic material, characterized in that a layer containing a water-soluble polymer having a molecular weight of 300,000 or more as a binder is inserted between the layer and the hydrophobic polymer layer. 3. A support is provided on one side with at least one silver halide emulsion layer having a hydrophilic colloid as a binder, the opposite side of the support having the silver halide emulsion layer provided thereon. On the side surface, a non-photosensitive hydrophilic colloid layer using a hydrophilic colloid as a binder, and a hydrophobic polymer layer composed of an aqueous dispersion of a hydrophobic polymer were coated on the outermost layer of the non-photosensitive hydrophilic colloid layer. A method for producing a silver halide photographic material, wherein the non-photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are provided on a support while simultaneously layering the non-photosensitive hydrophilic colloid layer, and subsequently dried. Providing a layer and the hydrophobic polymer layer on a support, drying and then storing in an atmosphere at a temperature of 20 ° C. or lower than the glass transition temperature of the hydrophobic polymer of the hydrophobic polymer layer. A method for producing a silver photographic photosensitive material. 4. The non-photosensitive hydrophilic colloid layer has a binder of gelatin and a thickness of 0.5 μm to 10 μm.
3. The silver halide photographic light-sensitive material according to claim 1, wherein the photographic material is less than m. 5. The thickness of the hydrophobic polymer layer is 0.5 μm.
3. The method for producing a silver halide photographic light-sensitive material according to claim 1, wherein the thickness is at least 10 [mu] m. 6. A support is provided on one side thereof with at least one silver halide emulsion layer having a hydrophilic colloid as a binder, the opposite side of the support having the silver halide emulsion layer provided thereon. A silver halide photographic light-sensitive material having a non-photosensitive hydrophilic colloid layer having a hydrophilic colloid as a binder on its side and a hydrophobic polymer layer formed on the outermost layer of the non-photosensitive hydrophilic colloid layer, In a manufacturing method in which a photosensitive hydrophilic colloid layer and the hydrophobic polymer layer are applied to a support while simultaneously stacking layers, and subsequently dried, the hydrophilic colloid layer has a charge and the hydrophobic polymer have The pH is adjusted so that the charges have the same sign, and the temperature difference between the dry-bulb temperature and the wet-bulb temperature of the drying air in the drying step is 7
C. or higher. 7. The binder for the non-photosensitive hydrophilic colloid layer is gelatin, and has a thickness of 0.5 μm to 10 μm.
The silver halide photographic light-sensitive material according to claim 5, which is less than m. 8. The hydrophobic polymer layer is composed of an aqueous dispersion of a hydrophobic polymer, and has a thickness of 0.5 μm to 10 μm.
The method for producing a silver halide photographic light-sensitive material according to claim 5, wherein