JPH07301886A - Photographic support and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photographic support having anticurl dependence on humidity in order to reduce its thickness in accordance with size reduction of cameras. CONSTITUTION:The photographic support has a laminate structure having a modified polyester layer containing a component, such as alkali metal isophthalic acid sulfonate, on the outside, and it curls in the widthwise direction in dependence on relative humidity, and the silver halide photographic sensitive material is obtained by forming photosensitive layers on this support and it satisfies the following related inequalities: 5X(G/D)X(0.5XH-60)<=K(H) <=5X(G/D)X(0.35XH-20) where H is a relative humidity (% RH); K(H) is a curl degree (m<-1>) under an environment of relative humidity H; G is the total amount of gelatin (g/m<2>) on the side of having the silver halide emulsion layers; and D is the film thickness (mum) of the support.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic support and a silver halide photographic light-sensitive material, and more specifically to a photographic support having an anti-curl humidity dependency in a wide humidity range and a curl using the same. Good and excellent in flatness,
The present invention relates to a silver halide photographic light-sensitive material excellent in handleability.

[0002]

2. Description of the Related Art At present, a compact camera which can be easily photographed and is convenient to handle and carry has been put into practical use.
However, considering the convenience and ease of carrying, further miniaturization is desired. In order to pursue miniaturization, it is essential to make the storage space of the built-in photographic film compact.

Usually, a photographic film is built in a state in which a roll-shaped film is sprinkled on a spool. Therefore, in order to make the space compact and to secure a fixed number of images (for example, 36 images), It is necessary to reduce the thickness of the film itself. In particular, the thickness of the photographic film support is currently 120-125 μm, which is considerably thicker than the thickness of the photosensitive layer (20-35 μm) above it. To do
It is considered to be the most effective means for reducing the thickness of the entire photographic film.

Incidentally, cellulose triacetate (hereinafter, abbreviated as TAC) is a typical support as the plastic film support conventionally used.
Roll-shaped photographic film is generally wound on a spool and built-in, and with a lapse of time after manufacturing, a curling habit is attached,
Therefore, the handling becomes difficult. In a photographic film having a TAC photographic support, the TAC photographic support easily absorbs water, and the curl attached to the TAC photographic support is removed when a development process is performed after photographing, and the film becomes substantially flat. However, the mechanical strength of the TAC photographic support is not so high originally, and when it is made thinner than the thickness of 135 format, the mechanical strength becomes weak and it becomes unsuitable as a photographic film support.

On the other hand, a polyester film has been conventionally used as an X-ray film or a plate-making film and has excellent mechanical strength. Therefore, by applying it to a photographic support, the thickness of the photographic film can be increased. Although it is possible to reduce the thickness, it is difficult to remove the film even if it is developed because it has almost no water absorption when it has a curl, which makes it difficult to handle.

Therefore, JP-A 1-244446 and 2-12
[0857] The specification of JP-A No. 8857 describes that by using a so-called modified polyester in which a hydrophilic component is introduced as a constituent component of the polyester, the curl after development can be easily taken. After development,
In addition, studies have been made on silver halide photographic light-sensitive materials that reduce the film thickness of the support to miniaturize the camera.

However, the silver halide photographic light-sensitive material using the TAC photographic support has various properties in addition to the above-mentioned properties of the support itself, that is, the excellent curl eliminating property after development processing. The present silver halide color photographic light-sensitive material is provided with a TAC photographic support, and thus the present photographic system is completed because it is provided. One of the excellent properties of a silver halide color photographic light-sensitive material having a TAC support is that the light-sensitive material is in a substantially flat state under a wide range of humidity conditions. This is because the TAC support itself has a humidity dependency of curl, and since an anti-curl can be easily imparted to the TAC support by a solvent of TAC, there is a humidity dependency of the photosensitive layer of the silver halide photographic light-sensitive material. Since the TAC support can have a force that antagonizes the contracting force, the curl balance can be maintained and the surface becomes almost flat.

Anti-curl processing of polyester photographic supports is not easy, but only certain special processing can make it possible. It is a method of applying a solution of a solvent to a polyester support to a polyester support, but this solvent is a phenol, which is very corrosive to humans and machinery and is dangerous, and the processed support is transparent. Property is lost, and the phenols remain in the support after processing, affecting the photographic performance, which is not a practical method. Moreover, the humidity dependence of the curl does not appear even if the support is simply anti-curled.

As one of the methods for adjusting the curl balance of a silver halide photographic light-sensitive material using a polyester photographic support such as polyethylene terephthalate, a support similar to the photosensitive layer is provided on the non-photosensitive layer side (back side) of the support. There is a method of providing a gelatin layer as a back layer. The disadvantage of this method is that when the silver halide photographic light-sensitive material is wound in a roll on a spool, particularly in the case of a small spool, the light-sensitive layer and the gelatin back layer may stick to each other, or the back surface in cine-type automatic processor processing may occur. It is not practical because the layer may be contaminated by roll marks and the thickness of the silver halide photographic light-sensitive material may be increased even if the support is thinned.

Further, Japanese Patent Laid-Open No. 123420/1975 describes the anti-curl of a polyester support in which two kinds of polyester films of the same kind having different intrinsic viscosities (for example, polyethylene terephthalate or polyethylene naphthalate) are laminated. Yes, but this is just an anti-curl method.

As described above, a polyester support such as polyethylene terephthalate or polyethylene naphthalate has a curl which cannot be removed even after development, and a silver halide photographic light-sensitive material using the same is not practical and is not very practical.

[0012]

In order to miniaturize the camera, there are many points in which the photographic support should be improved. For example, even if the support is thinned, the mechanical strength of the support is not small, the curl is easily eliminated after development, and the silver halide photographic light-sensitive material, that is, the photographic support, is almost flat under each relative humidity. Have an anti-curl that is humidity dependent. Among these, a problem that has not been solved to date is the development of a photographic support having an anti-curl that is humidity-dependent.

A first object of the present invention is to provide a photographic support having an anti-curl which is humidity dependent under a wide range of relative humidity, and a second object thereof is to be substantially flat even under a wide range of relative humidity. Another object of the present invention is to provide a silver halide photographic light-sensitive material capable of maintaining a stable state.

[0014]

Generally, a silver halide photographic light-sensitive material has a multilayer structure of a photographic support and a light-sensitive layer or a non-light-sensitive layer using gelatin as a binder.
The coated gelatin binder layer shrinks in low humidity and pulls the support with this layer inside to curl, while in high humidity, the gelatin binder layer expands and contracts weakly to flatten the support. If so, the silver halide photographic light-sensitive material has the property of becoming flat. The curl size of a silver halide photographic light-sensitive material is generally determined by the balance between the thickness of the support and its elastic modulus, and the thickness of the gelatin binder layer and its elastic modulus, and the gelatin binder itself shrinks considerably at low humidity and is large. To show the degree of curl (the thicker it gets, the bigger it gets). queue. Umberger's Photographic Science Engineering Vol. 1, p. 69, 1957 (JQ
Umberger: Phot.Sci.Eng., Vol.1, p.63, (1957)). The difference between the curl degree at low humidity and the curl degree at high humidity divided by the relative humidity difference is called the humidity dependence of curl.

Curling of the silver halide photographic light-sensitive material will be described. In a silver halide photographic light-sensitive material in which a silver halide emulsion layer (photosensitive layer) is coated on one side, an emulsion layer, an intermediate layer, a protective layer, etc. (hereinafter collectively referred to as a photosensitive layer) are coated. To bend to the side
Curling toward the non-photosensitive side (back layer side) is called (positive) curl and is called- (negative) curl.

The unprocessed TAC support itself generally has a + curl, and the degree of the curl increases from low relative humidity (for example, about 10% RH) to high relative humidity (+ curl). Becomes larger), 70% RH
The degree of curl increases abruptly at higher humidity. The continuous change in the degree of curl due to such relative humidity is called humidity dependence of curl. TAC support is TA
When the solvent for C is applied, it has the property of curling the applied side inward (concave). Utilizing this, a solvent is applied to the side opposite to the + (positive) curl of TAC to give a − (negative) curl (the degree of curl moves in parallel), which has humidity dependence − ( Negative) A curl can be imparted. That is, the − (negative) curl is large on the low relative humidity side, and the − (negative) curl is small on the high relative humidity side, or the degree of curl is zero, or the + (positive) curl is slight. Curling the side surface of the anti-photosensitive layer is called imparting anti-curl. In general, anti-curl processing itself does not have the property of imparting humidity dependency.

Since a polyethylene terephthalate (polyester) support has almost no hygroscopic property and is not sensitive to humidity, it is difficult to give such a support a property dependent on humidity.

The present inventor has focused on a modified polyester having a mechanical strength higher than that of a TAC photographic support and having a curl eliminating property after development, and if it has a curl eliminating property, it also depends on humidity. Therefore, various methods of imparting anti-curl having humidity dependency were investigated. As a result, the following problems were solved and the object could be achieved.

That is, the invention according to claim 1 is a support having a laminated structure of two or more layers having at least one polyester layer, wherein the support curls in the width direction and the curl depends on humidity. A laminated polyester photographic support characterized by having properties.

The invention according to claim 6 is a support having a laminated structure of two or more layers having at least one polyester layer, and curls in the width direction so that the side opposite to the photosensitive layer is concave. However, the curl has a laminated polyester photographic support having humidity dependence, at least one photosensitive layer is provided on the convex curl side of the support, and the following relational expressions are satisfied. And a silver halide photographic light-sensitive material.

5 × (G / D) × (0.5 × H-60) ≦ K (H) ≦
5 × (G / D) × (0.35 × H−20) [where, H is relative humidity (% RH), K (H) is curl degree (m ⁻¹ ) under relative humidity H environment, G represents the total amount of gelatin (g / m ² ) per unit area on the side having the silver halide emulsion layer, and D represents the thickness (μm) of the support.] Here, the curl degree is represented by 1 / R. , Its unit is m ^-1 . This R represents the radius of curvature of the curled film,
The unit is m (meter). Relative humidity H is usually RH%
It is represented by. The value measured under the environment of relative humidity H means that the sample is 1 under the environment of relative humidity H (RH%).
The value obtained by measuring the sample under the same relative humidity after humidity control for more than one day.

The present invention will be described in detail.

The polyester useful in the present invention is composed of polyethylene terephthalate or polyethylene naphthalate as a main constituent and a modified part in which the main chain is partially modified, and the modified part is an alkali metal sulfonate group. It is preferable to contain a structural unit having a side chain of. Further, a modified polyester having a constitutional unit having a side chain containing the alkali metal sulfonate group and a constitutional unit of polyalkylene glycol and / or a constitutional unit of aliphatic dicarboxylic acid in a main chain of the polyester is particularly preferable.

Here, the structural units will be described. Polycondensates such as polyesters are macromolecularized by the esterification or transesterification reaction of dibasic acid or its alkyl ester with divalent hydroxyl group. The molecule of dibasic acid or divalent hydroxyl group is a polymer molecule. The unit incorporated into the main chain of is referred to as a constitutional unit. The constitutional unit having a sulfonate group in the side chain is, for example, the isophthalic acid portion of sodium-isophthalic acid-5-sulfonate as the constitutional unit.

The constituent unit of polyethylene terephthalate, which is the main constituent part, is terephthalic acid, and the dicarboxylic acid as a constituent unit of polyethylene naphthalate includes 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid,
Examples of the naphthalenedicarboxylic acid such as 2,7-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid include
6-naphthalenedicarboxylic acid is preferred.

The glycol (diol) as a constituent unit of the main constituent part is ethylene glycol.

An acid component as a constituent unit of the modified portion,
That is, dibasic acids are terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, isophthalic acid, alkali metal-isophthalic acid- 5-sulfonate, alkali metal-isophthalic acid-4-sulfonate, alkali metal-2,6-naphthalenedicarboxylic acid-4-sulfonate, alkali metal-terephthalic acid-2-sulfonate, 1,4-
Cyclohexanedicarboxylic acid, adipic acid, sebacic acid and the like are preferable. The alkali metal of the alkali metal sulfonate substituent is preferably sodium, potassium, lithium, cesium and the like, with sodium being particularly preferred.

The modified portion preferably contains a constitutional unit having the above-mentioned alkali metal sulfonate group in the side chain, and the constitutional unit having the alkali metal sulfonate group in the side chain is 2,6-naphthalenedicarboxylic acid, Sodium-2,6-naphthalenedicarboxylic acid-4-sulfonate,
Sodium-isophthalic acid-5-sulfonate and the like are particularly preferable.

As the constitutional unit of the dibasic acid of the modified portion, a saturated aliphatic dicarboxylic acid as described above may be used together with the constitutional unit having the metal sulfonate group in the side chain, and among them, adipic acid is particularly preferable. .

As the glycols as the constitutional unit of the modified portion, in addition to ethylene glycol, propylene glycol, 1,4-butanediol, hexylene glycol, 1,4-
Benzene dimethanol, 1,4-cyclohexane dimethanol, 4,4'-bisphenol-2,2-propane, 1,4-cyclohexane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (number average molecular weight 300- 30,000), polypropylene glycol (number average molecular weight 300 to 30,000) and the like. Preferred glycols include ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol and the like, particularly ethylene glycol, polyethylene glycol (number average molecular weight 300 to 300,0
00) is preferred. The glycol unit of the ester bond in the modified portion is mostly ethylene glycol.

A modified polyester moiety having a constitutional unit having an alkali metal sulfonate group in its side chain and a polyethylene glycol constitutional unit and / or a saturated aliphatic dicarboxylic acid constitutional unit is useful in the present invention. In particular, a modified portion of a combination of sodium isophthalic acid-5-sulfonate and polyethylene glycol (number average molecular weight 300 to 300,000) and / or adipic acid is particularly preferable and useful.

The modified portion of the modified polyester useful in the present invention is 50 mol% or less based on the total polyester bonds, and when it exceeds 50 mol%, the physical properties as a support, such as mechanical strength, glass transition point, and water resistance. The properties are deteriorated and it becomes difficult to use as a support. It is preferably 40 mol% and particularly preferably 30 mol% or less.

The constitutional unit having an alkali metal sulfonate group in the side chain of the modified portion of the modified polyester useful in the present invention is 2 to the total ester bond also including the main constituent portion.
It should be contained in a proportion of 10 mol%. The presence of the constituent unit having the alkali metal sulfonate group in the side chain, for example, sodium-isophthalic acid-5-sulfonate responds to moisture / humidity, and helps the humidity dependence of anti-curl. Quantitatively, if it is 2 mol% or less, there is almost no humidity dependency, and if it is 10 mol% or more, the water absorption becomes too large and it becomes unsuitable as a support. It is preferably 2 to 7 mol%, and particularly preferably 3 to 6 mol%.

The modified portion of the modified polyester useful in the present invention, the polyalkylene glycol, is preferably 3 to 10% by weight based on the total weight of the polyester. This polyalkylene glycol, such as polyethylene glycol, has a fast response speed of water and seems to have a function of reacting sensitively to humidity dependency. If it is less than 3% by weight, the response will be slow, and if it is more than 10% by weight, water will be supplied too much to make it unsuitable as a support. Preferably the content is 4-8% by weight.

The saturated aliphatic dicarboxylic acid in the modified portion of the modified polyester useful in the present invention may be used with or without a polyalkylene glycol. Saturated aliphatic dicarboxylic acid, such as adipic acid, has a function of lowering the glass transition point of polyester, and seems to have a function of facilitating water supply of sulfonate groups. 3-10% by weight based on the total weight of polyester
If the amount is too large, the heat resistance is lowered and it becomes unsuitable as a support. The preferred content is 4 to 8% by weight, but when used together with polyalkylene glycol,
The content is preferably 3 to 10% by weight, particularly preferably 4 to 8% by weight.

As described above, the humidity dependence of the anti-curl of the laminated polyester photographic support of the present invention depends on the amount of the constituent unit having an alkali metal sulfonate group in the modified portion in its side chain, the amount of polyethylene glycol, and / or the saturated fat. It changes depending on the amount of group dicarboxylic acid, and the greater the amount, the greater the degree of humidity dependence. The desired humidity dependence of the anti-curl can be obtained by the quantitative combination of these two or three.

The modified polyester resin useful in the present invention can be synthesized by a conventionally known polyester production method. For example, in the esterification reaction, both direct esterification of an acid component with a glycol component and esterification by a transesterification method with glycol using an acid component as a dimethyl ester can be used. At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for esterification and a polymerization reaction catalyst such as antimony oxide in the polymerization reaction. Regarding the polyester components and the synthetic method described above, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), 103.
~ 136 pages, or "Synthetic Polymer V" (Asakura Shoten, 1971)
Year) You can refer to the description on pages 187-286.

Specific methods for synthesizing the modified polyester are described in US Pat. No. 4,217,441 and JP-A-5-210199, and the modified polyester useful in the present invention can be synthesized by these methods.

As described above, the laminated polyester photographic support of the present invention is a support having a laminated structure of two or more layers having at least one polyester layer, and the support curls in the width direction, The curl is characterized by having humidity dependency.

More specifically, the laminated polyester photographic support of the present invention is a laminated support in which at least one outer layer is a modified polyester layer, and the modified polyester layer is another polyester layer or another resin layer. It has a laminated structure of two or more layers. A laminated polyester photographic support in which a modified polyester layer useful in the present invention is laminated with another modified polyester layer of the same kind or another kind, or a resin layer such as another polyester, wherein the photographic support is The laminated structure on both sides of the support is asymmetrical with each other around the position where the support is bisected in the thickness direction. The laminated polyester photographic support has anti-curl in the width direction, the curl has humidity dependency, and satisfies the above formula.
The humidity dependence and the degree of curl of the anti-curl of the photographic support within the range of the above formula are changed by appropriately selecting and combining resin constituent components, resin properties, layer constitution, film forming conditions and the like. Designed by.

The term "asymmetry" as used herein means that they are physically, mechanically, or chemically different, and are made of different materials (totally different layers), the order in which the layers are formed, the thickness, and the constituents (common). The physical properties such as the type of the constitutional units of the polymerization), the amount of the constitutional components (the ratio of the constitutional units of the copolymerization) and the intrinsic viscosity are different.

As a method for measuring the asymmetry of these laminated films, various analytical instruments can be used.
Although not particularly limited, the cross-section of the film can be observed under a microscope and a micrograph can be taken regarding the layer structure. In addition, while observing the film under a microscope, each layer is scraped off, or the film is divided into halves, and each of the upper and lower layers is scraped from the upper and lower sides to obtain an analyte.
Hydrolysis and liquid chromatography or NMR
It may be measured by various measuring devices such as the like, or the inherent viscosity may be measured by NMR, GPC (gel permeation chromatography) or the like after the analyte is dissolved in a solvent, or the analyte may be powdered as it is. It is possible to measure IR (infrared spectroscopic instrument) etc. by mixing with X-ray spectroscopic instrument or KBr etc., and as a result, absolute amount or asymmetry in the difference in peak position, intensity etc. of the measurement result corresponding to it. Can be measured.

The layer structure of the laminated polyester photographic support of the present invention is preferably 2 or 3 layers, or may be a laminated structure of more layers.

When the laminated polyester photographic support of the present invention has a two-layer structure, the two layers forming the laminated support may be the modified polyester layer and other resin layers.
It is preferable that both layers are modified polyester layers, and it is more preferable that each of the two layers has different constituent components or different properties. The different constituents are different molecular weights, different copolymerization components, different copolymerization ratios, and the like.

When the laminated polyester photographic support of the present invention has a three-layer structure, the two outer layers are preferably the above-mentioned modified polyester layer. The central layer, as long as it does not impair the effects of the present invention, even if it is a polyester layer such as polyethylene terephthalate, polyethylene naphthalate, other materials, for example, polycarbonate, polyether, polyamide, polyimide, polyphthalamide, It may be polyphthalimide or the like. The most preferred layer structure is that all three layers are composed of modified polyester layers. It is preferable that the outer layers of the three-layer structure have different thicknesses, and when the thickness of each of the outer layers is d _A and d _B from the thicker side, the ratio d _A / d _B is preferably 1.1.
≦ d _A / d _B ≦ 5, particularly preferably 1.3 ≦ d _A / d _B ≦ 3
Is. Further, it is preferable that the modified polyesters of the outer layers of the laminated support have different copolymerization components or copolymerization ratios. Furthermore, the intrinsic viscosity of each resin may be different.

When the two outer layers are modified polyester layers,
When the contents of the copolymerization components or the intrinsic viscosities are almost the same, curling is performed so that the modified polyester layer side having a large film thickness becomes a concave surface. When the two outer modified polyester layers have substantially the same film thickness, the curl is such that the copolyester layer side having a large intrinsic viscosity or a large content of the copolymerization component becomes a concave surface. To do.

When the two outer layers are modified polyester layers and their intrinsic viscosities are different, the difference in intrinsic viscosities ΔIV is preferably in the range of 0.02 to 0.5, preferably in the range of 0.05 to 0.4, It is particularly preferably 0.1 to 0.3.

When the difference in intrinsic viscosity ΔIV is within the above range and the film thicknesses of the two outer layers are not so different from each other, curling is performed so that the outer layer side having a large intrinsic viscosity becomes a concave surface.

By properly adjusting the above items, anti-curl having humidity dependency is imparted in the width direction of the laminated support, and the desired degree of curl or degree of humidity dependency is obtained. It can be controlled arbitrarily.

Also in the case of the constitution of four or more layers, as in the case of the two and three layers, if the upper and lower layers are asymmetrical, a width curl can be imparted and the composition, the intrinsic viscosity, etc. can be imparted. By adjusting the physical properties, layer structure, thickness, manufacturing conditions, etc.,
Their degree can be controlled arbitrarily.

Here, the layer such as polyester layer means a film-like one having a certain thickness of resin as a support, and is distinguished from layers such as an undercoat layer, an antistatic layer and an emulsion layer. To be done.

The film formation of the laminated polyester photographic support of the present invention can be carried out in the same manner as in the conventionally known method of polyethylene terephthalate except the laminating process.

The laminated polyester photographic support of the present invention having a laminated structure of two or more layers can be produced as follows. That is, for example, a method for producing a laminated film of polyethylene terephthalate and a modified polyester is as follows.
Melt extruded through multiple extruders and filters controlled in the temperature range of up to 320 ° C, and then melt extruded into a sheet by joining them in a laminar flow in a molten polymer conduit or an extrusion die. , A co-extrusion method in which after solidification by cooling on a rotating cooling drum to obtain an unstretched film, the unstretched film is biaxially stretched in the longitudinal direction and the transverse direction, heat setting, relaxation treatment, or polyethylene terephthalate or modified Melt extrusion of polyester single layer and laminated film from an extruder, and cooling or solidifying on a cooling drum, an unstretched film or a uniaxially oriented film surface obtained by uniaxially stretching the unstretched film is coated with an anchor agent, an adhesive, etc., if necessary. Extrusion lamination of polyethylene terephthalate or modified polyester single layer and laminated film , Then there are such extrusion lamination method of thermally fixed after completing the biaxially oriented, co-extrusion from simplicity of process is preferred.

In this case, the stretching condition of the film is not particularly limited, but in general, the film is stretched biaxially in a temperature range of Tg + 100 ° C. from Tg having a higher glass transition temperature (Tg) of polyethylene terephthalate or the modified polyester layer. To do. At this time, the following methods A, B, and C can be adopted in the same manner as the stretching method of the single-layer polyethylene terephthalate.

(A) A method in which an unstretched sheet is first stretched in the machine direction and then stretched in the transverse direction.

(B) A method in which an unstretched sheet is first stretched in the transverse direction and then in the longitudinal direction.

(C) A method in which an unstretched sheet is stretched in the longitudinal direction in one stage or in multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction. The stretching ratio is preferably in the range of 4 to 16 times in area ratio. The heat setting can be performed in the temperature range of 150 to 240 ° C.

At that time, by appropriately setting the stretching condition temperature, heat setting temperature, relaxation rate, etc., the size of the anti-curl after film formation of the laminated polyester photographic support of the present invention is appropriately changed, You can control.

The degree of anti-curl and its humidity dependency of the laminated polyester photographic support of the present invention are shown in FIGS. 1, 2, 3, 5 and 7 of the following Examples. That is, if the curl degree is about -10 to -55 at a relative humidity of 10% RH and the curl degree is about +10 to -25 at a relative humidity of 70% RH, a photosensitive layer (emulsion layer, etc.) to be applied later is provided. Thickness is 5
When it is about 30 μm, a flat silver halide photographic light-sensitive material with a small curl can be obtained.

For the support, a matting agent, an antistatic agent, a slip agent, a surfactant, a stabilizer, an antioxidant, a dispersant, a plasticizer, an ultraviolet absorber, an anti-tacking agent, a softening agent, a fluidizing agent, etc. You may add.

The above-mentioned antioxidant is not limited to its kind, and specific examples thereof include hindered phenol compounds, allylamine compounds, phosphite compounds and thioester compounds, and commercially available products can be used. . Among these, hindered phenol type is preferable. In producing the MP support, it is most effective and preferable to add the antioxidant before extrusion. In order to obtain excellent photographic performance without increasing the turbidity of the MP support, its content is usually 0.01 to 2% by weight, preferably 0.1 to 0.5% by weight, based on the MP. . The antioxidants may be used alone or in combination of two or more.

Further, a phenomenon called light piping in which light incident from the cross section of the photographic film propagates inside the support and penetrates deep into the film is apt to occur, but when this occurs, unnecessary fog occurs in the emulsion layer. In order to prevent this phenomenon, a dye may be added to the support for coloring. When the support is polyester, this dye is preferably a heat-resistant dye that can withstand the melt film formation method. In the case of a color photographic film, this coloring is preferably gray. As the dye, one kind or a mixture of two or more kinds may be used. For example, this target can be achieved by using a dye such as DIARESIN manufactured by Mitsubishi Kasei Co., Ltd., or MACROLEX manufactured by Bayer Co. alone or in an appropriate mixture.

The thickness of the laminated polyester photographic support of the present invention is, for example, 40 to 150 in terms of the thickness of a general support.
Although it can be used in the range of μm, anti-curl is preferably within the range of the formula of the present invention in view of miniaturization of the camera.
˜105 μm, more preferably 50 to 90 μm.

The total amount of gelatin per unit area (1 m ² ) on the side having the silver halide emulsion layer of the present invention (unit:
The g / m ² ) is not particularly limited as long as the anti-curl is set within the range of the formula of the present invention, but is preferably
It is 5 to 30 g / m ² , and more preferably 10 to 25 g / m ² .

<Undercoat layer> An undercoat layer is used for coating and adhering the emulsion layer to the laminated polyester photographic support of the present invention. This undercoating method is exactly the same as that of a conventional polyethylene terephthalate support. Can be done in any way.

That is, the undercoat layer of the polyester support is generally coated with a water-based polymer latex before or after stretching during film formation. An organic solvent system containing a so-called etching solvent (for example, phenol, cresol, resorcin, chloral hydrate, chlorophenol, etc.) for applying or etching polyethylene terephthalate (hereinafter abbreviated as PET) to bond the subbing material by the anchoring effect. Alternatively, there is a method of applying a water-based undercoat liquid. This is PE
This is because T has a regular structure that does not easily adhere, and it is necessary to change this surface structure loosely or chemically. Mechanical processing for this,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
Surface activation treatment such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone treatment may be performed. Good adhesive strength can be obtained by directly coating the photographic emulsion after the above treatment, but in order to further strengthen the adhesive strength, a further subbing layer may be provided, and a photographic emulsion layer may be formed on the undercoating layer. A good film is obtained. Even with a water-based undercoating agent, the adhesiveness can be easily improved by utilizing the above various treatments as a pretreatment. For example, JP-A-55-67745,
N-Butyl methacrylate: a quaternary copolymer latex composed of t-butyl methacrylate, styrene and 2-hydroxyethyl methacrylate, a surfactant, and a water-based subbing comprising a curing agent according to the method described in JP-A-59-19941. It is possible to obtain a light-sensitive material having good adhesiveness by applying the solution, drying it, and then subjecting it to corona discharge treatment again, and then applying an aqueous gelatin solution such as an antihalation layer or emulsion layer to the photographic emulsion layer side. it can. The antistatic layer side on the opposite side is subjected to the same treatment or an undercoat layer as described above, and then directly coated with an antistatic composition, or with an antistatic composition such as cellulose diacetate previously coated with a binder. A desired photographic light-sensitive material can be finished by applying the product as an organic solvent system liquid. The modified polyester support of the present invention can be subbed in the same manner.

<Back Layer or Antistatic Layer> A layer provided on the opposite side of a photosensitive material having a photosensitive layer on one side without the photosensitive layer is called a back layer. The back layer is usually provided with an antistatic layer. In general, PET or the like is subjected to the above-mentioned subbing and then a back layer such as an antistatic layer is applied.

In the antistatic layer useful in the present invention, most of the antistatic agents and antistatic compositions generally useful for silver halide photographic light-sensitive materials can be used. For example,
Styrene described in No. 47-28937 or Japanese Patent Publication No.
Anionic polymer antistatic agent such as sodium maleate copolymer, sodium vinylbenzyl sulfonate copolymer described in JP-A-53-82876, sodium styrene sulfonate copolymer described in JP-B-48-23451 Agent; JP-A-51-4
2535, JP-A-54-159222 and JP-A-55-7763, ionene polymers (for example, a polymer of triethylenediamine and xylidene dichloride), US Pat. No. 2,882,
No. 157, for example, polymethacryloylethyldiethylmethylammonium methylsulfonate, JP-B-60-516
No. 93, JP-A-61-223736 and JP-A-62-9346, a cross-linked copolymer particle having a quaternary ammonium group in its side chain (for example, copolymer [N, N, N-trimethyl-N -Vinylbenzylammonium chloride-co-divinylbenzene]), cationic antistatic agents such as ionene polymer cross-linking type or copolymer particles having an ionene polymer as a side chain described in Japanese Patent Application No. 5-174572 (for example, polyvinyl Cross-linking reaction product of benzyl chloride and terminal N- (polymer of triethylenediamine and xylidene dichloride), Japanese Patent Publication
Alumina sol described in 57-12979 as a main component,
JP 57-104931 Patent ZnO _{according, SnO 2, TiO 2, Al} 2 O 3, In 2
_{O 3, SiO 2, MgO,} BaO, MoO 3, ZiO particulate metal oxides such as _2, V ₂ O ₅ or the like of the metal oxide antistatic agent described in JP-B-55-5982, described in JP-B-52-32572 Higher fatty alcohol phosphate ester antistatic agent, poly- (5-dodecylbenzothiophene), poly- (3-dodecylthiophene), and metacloylethyloxymethyl described in JP-A-2-255770 or JP-A-2-308246 Examples thereof include polythiophene-based polymers such as 3-polythiophene, and conjugated double bond conductive polymers such as poly (isothianaphthene) -based polymers described in JP-A-2-252726.

If necessary, a back layer may be applied to the back surface. A hydrophilic binder layer may be used as the back layer. As the hydrophilic binder, gelatin, which is similar to the binder for the photosensitive layer, is most preferably used, and various gelatins are used. Other hydrophilic colloids, matting agents, slip agents, surfactants, hardeners, dyes, thickeners, polymer latices, antistatic agents and the like can be added as required.

<Photosensitive layer such as silver halide emulsion layer> As the silver halide photosensitive material according to the present invention, an ordinary black-and-white photographic light-sensitive material (for example, black-and-white light-sensitive material for photographing, black-and-white light-sensitive material for printing, black-and-white light-sensitive material for X ray) Materials, etc.), ordinary multilayer color light-sensitive materials (eg color negative film, color reversal film, color positive film, etc.)
Various light-sensitive materials can be mentioned. It is particularly effective for high-sensitivity silver halide light-sensitive materials and high-speed rapid processing silver halide light-sensitive materials. Specifically, they are roll films of color negative, positive, reversal light-sensitive materials and the like, roll films of X-ray black and white light-sensitive materials for indirect photography and the like.

Silver halide grains and other additives of the silver halide emulsion used in the silver halide light-sensitive material of the present invention, for example, chemical sensitizers, spectral sensitizing dyes, hardeners, surfactants, color couplers, There are no particular restrictions on etc.,
For example, Research Disclosure
osure) No. 308119 (hereinafter abbreviated as RD308119) can be used. The description location is shown below.

[Item] [Page of RD308119] Iodine composition 993 IA Item Manufacturing method 〃 〃 and 994 E Item Crystal habit Normal crystal 〃 Twin crystal 〃 〃 Epitaxial 〃 〃 Halogen composition Uniform 993 IB Item uniform Not 〃 Halogen conversion 993 I-C item Halogen substitution 〃 Metal-containing 993 I-D item Monodisperse 995 I-F item Solvent addition 〃 Latent image forming surface 995 I-G inner surface 〃 Applied photosensitive material Negative 995 Item IH Positive (including internal fog grains) 〃 〃 Mixed emulsion 995 IJ Item Desalting 995 II-A Item The silver halide emulsion was subjected to physical ripening, chemical ripening and spectral sensitization. Use one. Additives used in such processes, Research Disclosure No. 17643,
Same No. l8716 and same No. 308119 (hereinafter referred to as RDl7643,
(Abbreviated as RDl 8716 and RD308119). The description location is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A, B, C, D, 23 to 24 648 to 9 E ~ J Item Supersensitizer 996 IV-A ~ E, J item 23 ~ 24 648 ~ 9 Antifoggant 998 VI 24 ~ 25 649 Stabilizer 998 VI 24 ~ 25 649 The photographic additives that can be used are also in the above RD. Have been described.
Descriptions are shown below [Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII-C 25-26 XIII-C Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer 1011 XX-B (included in the photosensitive material) Also use various couplers And specific examples thereof are also described in the above RD. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item 25 VII-C to G item Magenta coupler 1001 VII-D item 25 VII-C to G item Cyan coupler 1001 VII-D item 25 VII-C to G Colored coupler 1002 VII-G 25 VII-G DIR coupler 1001 VII-F 25 VII-F BAR coupler 1002 VII-F Other 1001 VII-F useful residue releasing coupler Alkali Soluble 1001 VII-E coupler The additives used can be added by the dispersion method described in RD308119XIV.

For the color light-sensitive material, the above-mentioned RD308119 VII-
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided. In addition, the above-mentioned RD308,119 VII-K
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section can be adopted.

Development processing of the silver halide photographic light-sensitive material of the present invention is carried out, for example, by T.W. H. James, Theory of the Photographic Process 4th Edition (Th
e Theory of The Photographic Process Forth Editio
n) Pages 291 to 334, and Journal of the
American Chemical Society (JournaI of the A
American Chemical Society) Vol. 73, p. 3,100 (195
The known developer described in 1) can be used. The color photographic light-sensitive material is the same as RD17,6 described above
43, pages 28-29, RDl8, 716, page 615 and RD308, 119, XI
The development process can be carried out by a usual method described in X.

<Magnetic Recording Layer> If necessary, the silver halide photographic light-sensitive material may be coated with a magnetic recording material on the upper surface of the photosensitive layer or on the upper surface of the back layer for the following purposes.

For example, a stripe-shaped magnetic recording layer in which fine ferromagnetic particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and shooting conditions. KAISHO 50-62627 publication, JP 49-4503 publication,
U.S. Pat. Nos. 3,243,376 and 3,220,843, etc., and a transparent magnetic recording on the back surface of a photographic light-sensitive material with the required transparency by selecting the amount and size of magnetic particles. Providing layers is US license No. 3,782,947
No. 4,279,945, No. 4,302,523, and the like. Further, in U.S. Pat.No. 4,947,196 and WO90 / 04254, there is described a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material that enables magnetic recording on the back surface of the photographic film. Has been done.

As described above, the silver halide photographic light-sensitive material contains various kinds of information on the photographic light-sensitive material such as the type / manufacturing number of the photographic light-sensitive material, the manufacturer's name and the emulsion No. , Exposure time, lighting conditions, filter used, weather, size of shooting frame, camera model, use of anamorphic lens, and other various information at the time of camera shooting, for example, number of prints, selection of filter, customer Various information necessary for printing, such as the color preference and trimming frame size, for example, the number of prints,
Entering various information obtained at the time of printing such as filter selection, customer's color preference, trimming frame size, and other customer information is important for management and print quality improvement. It is convenient if the above-mentioned matters are recorded in order to improve the efficiency of printing work.

In the conventional photographic light-sensitive material, it is impossible to input all of these information, and
At the time of shooting, I was only optically entering information such as the shooting date / time, aperture, and exposure time. Moreover, at the time of printing, it was completely impossible to input the above information into the photographic light-sensitive material because there was no means for that.

Since the magnetic recording method is easy to record / reproduce, the use of the magnetic recording method for inputting the above various information to the photographic light-sensitive material has been studied, and various techniques have been proposed as described above. There is.

By providing these magnetic recording layers, it becomes possible to record the above-mentioned various kinds of information in the photographic light-sensitive material, which has been difficult in the past, and it is possible to record voice and image signals. is doing.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-deposited iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder, etc. are used. it can.

When the transparent magnetic recording layer is provided on the photosensitive layer side, a hydrophilic binder such as gelatin is used as the binder of the magnetic recording material. In the case of a hydrophilic binder, gelatin is preferably used. When the magnetic recording layer is provided on the back side without the photosensitive layer, a hydrophobic solvent-soluble binder such as cellulose nitrate is used.

[0085]

EXAMPLES Examples of the present invention will be described in detail below.
It goes without saying that the present invention is not limited to this.

Examples 1 to 3 <Production of Laminated Polyester Photographic Supports 1 to 5> Laminated polyester photographic Supports 1 to 5 were produced by the following method.

100 parts by weight of dimethyl terephthalate, 64 parts by weight of ethylene glycol, and 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst were added to carry out a transesterification reaction by a conventional method.

The product obtained was added with sodium- (β-hydroxyethyl) isophthalic acid-5-sulfonate (abbreviation;
SIP) ethylene glycol solution (concentration 35% by weight) 28
Parts by weight and polyethylene glycol (abbreviation: PE
G) (Number average molecular weight: 3000) 8.1 parts by weight was added, followed by 0.05 parts by weight of antimony trioxide, 0.13 parts by weight of phosphoric acid trimethyl ester, and Irganox 1 as an antioxidant.
0.2 parts by weight of 010 (manufactured by CIBA-GEIGY) and 0.02 parts by weight of sodium hydroxide were added. Then the temperature is gradually raised and the pressure is reduced, and polymerization is carried out under the conditions of 280 ° C. and 0.5 mmHg to obtain an intrinsic viscosity of 0.5.
A modified polyester of 5 was obtained.

Using the modified polyester and photographic polyethylene terephthalate (intrinsic viscosity: 0.65) used as the polyester layer, a laminated polyester photographic support was obtained as follows.

The above modified polyester and polyethylene terephthalate were vacuum dried at 150 ° C., respectively, and then 2
Melt extrusion at 285 ° C. using a single extruder, and layered in the T-die from the side of the support where the photosensitive layer is coated so that the thickness ratio of polyethylene terephthalate / modified polyester is the layer configuration shown in Table 1. And was rapidly cooled and solidified on a cooling drum to prepare a polyester laminated unstretched film. This laminated unstretched film was stretched 3.5 times in the vertical direction at 85 ° C., and further stretched 3.5 times in the horizontal direction at 95 ° C.
Heat-fixed at the temperature shown in Table 1, the relaxation rate was changed as shown in Table 1, and 90 μm thick laminated polyester photographic support 1 to 5
Got

<Preparation of Photosensitive Material><Undercoat Layer and Antistatic Layer> Corrosion discharge of 8 W / (m ² · min) was applied to both surfaces of the above-mentioned laminated polyester photographic supports 1 to 5 to apply to the photosensitive layer coated side. The undercoat coating solution B-1 was dried to a film thickness of 0.
The subbing layer B-1 is formed by coating so as to have a thickness of 8 μm, and the subbing coating solution B-2 below is dried on the other surface of the support to give a dry film thickness of 0.
The undercoat layer B-2 was formed by coating so as to have a thickness of 8 μm.

<< Undercoating Liquid B-1 >> Copolymerized latex liquid (solid content 30%) 270 g Butyl acrylate 30% by weight t-Butyl acrylate 20% by weight Styrene 25% by weight 2-Hydroxyethyl acrylate 20% by weight Compound ( UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml << Subbing coating solution B-2 >> Copolymer latex solution (solid content 30%) 270 g Butyl acrylate 40% by weight Styrene 20% by weight Glycidyl acrylate 40% by weight Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml Furthermore, undercoat layer B-1 and undercoat layer B-2 On top of 8W / (m ²
-Min) corona discharge is applied, and on the undercoat layer B-1,
The undercoat layer B-3 is formed by applying the following coating liquid B-3 to a dry film thickness of 0.1 μm, and the undercoat layer B-2 has the following coating liquid B-4 on the dry film thickness. The undercoat layer B-4 having an antistatic function was formed by coating so as to have a thickness of 0.1 μm.

<< Coating Liquid B-3 >> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Finish with water 1000 ml << Synthesis method of tin oxide-antimony oxide composite dispersion >> 230 g of stannic chloride hydrate and 23 g of antimony trioxide were dissolved in 3000 ml of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution became 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours, and a reddish brown colloidal precipitate was separated by centrifugation. The precipitate was washed many times with distilled water to remove excess ions. 200 g of colloidal precipitate from which excess ions were removed was redispersed in 1500 ml of water and sprayed in a firing furnace heated to 800 ° C to give an average particle size of 0.2.
A μm tin oxide powder was obtained. The crystallite size of this powder is 4
The volume resistivity was 1.5 nm and the volume resistivity was 1 × 10 ² Ωcm. This powder 40
A mixed solution of 0 g and 600 g of water was adjusted to pH 7.0, and Dispersion A was adjusted with a stirrer and a sand mill.

<< Coating Liquid B-4 >> Gelatin 10 g Copolymerized latex liquid (solid content 30%) (below) 270 g Butyl acrylate 40 wt% Butylene 20 wt% Glycidyl acrylate 40 wt% Compound (UL-1) 0.6 g Hexamethylene -1,6-bis (ethylene urea) 0.8g Dispersion A (dispersion of conductive particles) Particles 200g Equivalent amount Finish with water 1000ml 25W / (m ² · min) on the undercoat layer B-3 Corona discharge was applied, and 8 W / (m ² · min) on the undercoat layer B-4.
Was subjected to corona discharge. Further, the following emulsion layers and the like are sequentially formed on the surface of the undercoat layer B-3 and the following back layer is formed on the surface of the undercoat layer B-4, and a magnetic recording material is provided on the back layer. Silver photographic light-sensitive material samples 001 to 005 were prepared.

<Back Layer> First Layer The components below were mixed together with a dissolver and then dispersed with a sand mill to obtain a dispersion liquid. It was applied so as to have a dry film thickness of 2 μm.

Nitrocellulose 35 parts by weight Polyurethane resin 35 parts by weight Lauric acid 1 part by weight Oleic acid 1 part by weight Butyl stearate 1 part by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co Coated γ-Fe ₂ O ₃ (Long width 0.2 μm, short axis 0.05 μm, Hc = 650 oersted) 5 parts by weight Second layer The following coating liquid was applied onto the first layer so that the concentration was 10 ml / m ² .

Carnauba wax 1 g Toluene 700 g Methyl ethyl ketone 300 ml The above UL-1, UL-2 and UL-3 are shown below.

[0098]

[Chemical 1]

<Photosensitive layer> First layer; antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 2.3 g Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / Silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) ) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR conversion Substance (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye ( S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil- 1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 1.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.6 g silver iodobromide emulsion (average particle size 0.3 [mu] m, an average iodide content of 2.0 mol%) 0.2 g sensitizing dye (S-4) 6.7 × 10 -4 ( mol / silver model ) Sensitizing dye (S-5) 0.8 × 10 -4 ( mol / mole of silver) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR Compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye ( S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) ) 0.004g High boiling point solvent (Oil-2) 0.35g Gelatin 1.0g 8th layer; Yellow filter layer (YC) Yellow Colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g 9th layer; low Sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR Compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) 0.5 g sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of silver) sensitizing dye (S-11) 1.2 × 10 -4 ( mol / 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 2.0 g 11th layer; 1st protective layer (PRO-1) Iodobromide Silver emulsion (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High Boiling point solvent (Oil-1) 0.07g High boiling point solvent (Oil-3) 0.07g Gelatin 1.4g 12th layer; 2nd protective layer (PRO-2) Compound (Compound A) 0.04g Compound (Compound B) 0.004g Poly Methyl methacrylate (average particle size: 3 μm) 0.02 g Cylmethacrylate: Ethyl methacrylate: Methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13 g Gelatin 1.4 g << Preparation of silver iodobromide emulsion >> Silver iodobromide emulsion used for the 10th layer It was prepared by the following method.

A silver iodobromide emulsion was prepared by the double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

Solution (G-1) having the following composition: temperature 70 ° C., pAg
While maintaining the pH at 7.8 and pH 7.0, a seed emulsion corresponding to 0.34 mol was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, a solution (H-1) having the following composition and a solution (S-
1) and 1) were added over 86 minutes at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) while maintaining a flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase-) Subsequently, while maintaining the pH at 10.1 and the pH at 6.0, (H-2) and (S
-2) was added at a flow rate of 1: 1 (accelerating flow rate at the end was 5.2 times the initial flow rate) for 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them, and the pH is adjusted to 40 ° C.
And pAg were adjusted to 5.8 and 8.06, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

(G-1) Solution Ocein gelatin 100.0 g 10% by weight solution of the following compound-I in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml * Compound-I: polypropyleneoxy -Polyethyleneoxy-sodium di-succinate (H-1) solution ossein gelatin 82.4g potassium bromide 151.6g potassium iodide 90.6g finishing with water 1030.5ml (S-1) solution silver nitrate 309.2g 28% aqueous ammonia solution equivalent water Finishing 1030.5 ml (H-2) solution Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finishing with water 3776.8 ml (S-2) solution Silver nitrate 1133.0 g 28% ammonia solution equivalent Finishing with water 3776.8 ml No. 10 For silver iodobromide emulsions used in emulsion layers other than the above layers, the average grain size of seed crystals, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing H, flow rate, addition time, and halide composition.

All were core / shell type monodisperse emulsions having a distribution width of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material further comprises compounds Su-1, Su-2, a viscosity modifier, a film hardener H-1, and H-.
2, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight-average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1
(9.4 mg / m ² ) included.

The structural formulas of the compounds contained in the above formulation liquid are shown below.

[0110]

[Chemical 2]

[0111]

[Chemical 3]

[0112]

[Chemical 4]

[0113]

[Chemical 5]

[0114]

[Chemical 6]

[0115]

[Chemical 7]

[0116]

[Chemical 8]

[0117]

[Chemical 9]

[0118]

[Chemical 10]

[0119]

[Chemical 11]

The total amount of gelatin (g / m ² ) per unit area (1 m ² ) on the side having the silver halide photosensitive layer was 17 g / m ^2.
Met.

The evaluations described below were carried out. Table 1 shows the film-forming conditions of the laminated polyester photographic support (hereinafter abbreviated as "support"), the thickness of the support and the coating amount (coating amount) of gelatin on the photosensitive layer. The results of the scratch test are shown in Table 1, the curl degree of the support is shown in FIG. 1, and the curl degree of the silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material) is shown in FIG.

<Test Method and Evaluation Method><< Method of Measuring Curling Degree of Support >> With the uncoated support as it is, and for the photosensitive material samples 001 to 005, the photosensitive layer was peeled off using pancreatin, In addition, the back layer,
After the undercoat layer was peeled off using acetone, 8 sets of each sample were cut and formed with a width of 35 mm in the width direction of the film and a width of 2 to 3 mm in the longitudinal direction. 23 ℃, 10-80% R
After humidity was adjusted for 72 hours in an environment of H (10% RH interval), the curl degree in the width direction was measured in each environment.

<< Evaluation Method of Curling Degree of Photosensitive Material >> For the photosensitive material samples 001 to 005, 35 mm in the width direction of the film,
Eight sets of each sample were cut and formed with a width of 2 to 3 mm in the longitudinal direction. Each of them was conditioned for 72 hours in an environment of 23 ° C. and 10 to 80% RH (10% RH interval), and then the curl degree in the width direction was measured in each environment.

If the curl degree of the light-sensitive material exceeds +20 m ^-1 , the back layer side becomes extremely convex, so that the back layer side is liable to be scratched in the camera, during printing, etc., which is a problem. On the other hand, when the curl degree exceeds -10 m ^-1 , the photosensitive layer side becomes convex, so that scratches, pressure fogging, etc. are likely to occur on the photosensitive layer, which is a problem.

<Scratch test> 13 of photosensitive material samples 001 to 005
I cut it into a shooting length equivalent to 36 frames in 5 sizes and loaded it into the camera. After humidity was controlled for 1 day in an environment of 10% RH at 23 ° C. and 80% RH at 23 ° C., the image was photographed, and the occurrence of scratches and the like generated in the print after development was evaluated.

A: No scratches or the like are found.

Δ: Slight scratches and the like are observed.

X: Scratches and the like are considerably generated.

If it is ◯, there is no practical problem.

[0130]

[Table 1]

<Evaluation Results> Table 1 shows the results of curl degree measurement.
This is shown in FIGS. FIG. 1 shows the curl degree of the support after coating the undercoat layer, the photosensitive layer, the back layer, etc., and peeling these layers from the photosensitive materials 001 to 005. It was confirmed that the curl degree was the same as that of 5. Further, as shown in FIG. 1, by changing the conditions of the support and designing the humidity dependence of the anti-curl within the optimum range of the present invention to prepare the support, as shown in FIG. The curl size of the light-sensitive material is also within the preferable range of +20 to -10 m ^-1 , and it can be seen that as shown in Table 1, generation of scratches is prevented.

Examples 4 to 6 Using the same modified polyester as in Examples 1 to 3, three extruders and a three-layer laminated T-die were used, and the heat setting temperature and relaxation rate were set to the conditions shown in Table 2. Otherwise, the supports 6 to 10 were prepared by the same method as in Examples 1 to 3, and the undercoat layer was prepared in the same manner as in Examples 1 to 3.
Photosensitive materials 006 to 010 were prepared by providing a photosensitive layer and a back layer. The evaluation method and the test method were the same as in Examples 1 to 3. The results are shown in Table 2, FIG. 1 and FIG.

[0133]

[Table 2]

As shown in FIG. 3, if the layer structure of the support is changed so that the temperature dependence of the anti-curl is designed within the optimum range of the present invention, as shown in FIG. The curl size is also within the preferable range of +20 to -10 m ^-1 , and it is understood that the occurrence of scratches is prevented as shown in Table 2.

Examples 7 to 8 Substrates 7 and 9 were provided with an undercoat layer and a back layer in the same manner as in Examples 1 to 3, and the total amount of gelatin in the photosensitive layers of Examples 1 to 3 was set.
Light-sensitive material samples 011 to 013 were prepared by changing the coating amount from 17 g / m ² to 10 g / m ² as follows. 1.7 g / m ² gelatin amount of the second layer of the photosensitive layer, the first layer and the 10th layer of 0.7 g / m ^2, 3
Layer and 4th layer 0.1g / m ² , 5th layer 1.3g / m ² , 11th layer
The total amount of gelatin on the side of the photosensitive layer was reduced to 1.0 g / m ² , and the twelfth layer was reduced to 0.9 g / m ² , respectively, so that the total amount of gelatin on the side of the photosensitive layer was 10 g / m ² .

In the same manner, the curl degree of the support and the curl degree of the photosensitive material were measured, and the scratch test and evaluation were performed. The results are shown in Table 3, FIG. 5 and FIG.

[0137]

[Table 3]

The support 8 in FIG. 5 is the same support as in Example 6, but when the total amount of gelatin in the photosensitive layer is set to 10 g / m ² , it deviates from the scope of the present invention, and the curl degree is low on the low humidity side. Below 10 will cause scratches. Thus, the humidity dependence of the anti-curl of the support is designed within the optimum range of the present invention, and if the total amount of gelatin / the thickness of the support within the scope of the present invention is set, as shown in FIG. The curl size is + 20-
It is within the preferable range of 10 m ⁻¹ , and as shown in Table 3, it can be seen that scratches are prevented.

Examples 9 to 10 Supports 11 to 14 were prepared in the same manner as the supports 6 to 9 except that the thickness of the support was 70 μm. Emulsion layers were coated in the same manner as in Examples 4 to 6 to prepare photographic light-sensitive material samples 014 to 017. At that time, changing the total amount of gelatin of the photosensitive layer to 12 g / m ² (second layer 1.7 g / m ^2, the fifth layer 1.3 g / m ^2, the 11th layer
1.0 g / m ² , the twelfth layer was 0.9 g / m ² , and the weight was reduced respectively.

In the same manner, the curl degree of the support and the curl degree of the photosensitive material were measured, and the scratch test and evaluation were performed. The results are shown in Table 4, FIG. 7 and FIG.

[0141]

[Table 4]

Even when the thickness of the support was changed to as thin as 70 μm and the total amount of gelatin in the photosensitive layer was set to 12 g / m ² , as shown in FIG. If it is designed so as not to have an optimum area, the curl size of the light-sensitive material is within a preferable range of +20 to -10 m ^-1 as shown in FIG. 8, and the occurrence of scratches is prevented as shown in Table 4. I understand.

[0143]

According to the present invention, a laminated polyester photographic support having an anti-curl humidity dependency within the scope of the present invention, and a flat support over an almost wide humidity range having the support and having excellent handleability. A silver halide photographic light-sensitive material can be provided.

[Brief description of drawings]

FIG. 1 is a relationship diagram of relative humidity and anti-curl degree of a laminated polyester photographic support.

FIG. 2 is a graph showing the relationship between relative humidity and curl of a silver halide photographic light-sensitive material having a laminated polyester photographic support.

FIG. 3 is a diagram showing the relationship between relative humidity and anti-curl degree of a laminated polyester photographic support.

FIG. 4 is a graph showing the relationship between relative humidity and curl of a silver halide photographic light-sensitive material having a laminated polyester photographic support.

FIG. 5 is a relationship diagram of relative humidity and anti-curl degree of a laminated polyester photographic support.

FIG. 6 is a diagram showing the relationship between relative humidity and curl of a silver halide photographic light-sensitive material having a laminated polyester photographic support.

FIG. 7 is a diagram showing the relationship between relative humidity and anti-curl degree of a laminated polyester photographic support.

FIG. 8 is a relationship diagram of relative humidity and curl degree of a silver halide photographic light-sensitive material having a laminated polyester photographic support.

Claims (10)

[Claims] 1. A support having a laminated structure of two or more layers having at least one polyester layer, wherein the support curls in the width direction and the curl has humidity dependency. A laminated polyester photographic support. 2. The laminated polyester photograph according to claim 1, wherein at least one of the polyester layers is a layer of modified polyester containing a constitutional unit having an alkali metal sulfonate group in a side chain in a main chain. Support. 3. The laminated polyester photographic support according to claim 1, wherein the constituent unit having an alkali metal sulfonate group in its side chain is an alkali metal aromatic dicarboxylic acid unit. 4. At least one of the polyester layers is a layer of a modified polyester containing an alkali metal aromatic dicarboxylic acid sulfonate unit and a polyalkylene glycol unit and / or an aliphatic dicarboxylic acid unit in the main chain. The laminated polyester photographic support according to claim 1. 5. The laminated polyester photographic support according to claim 4, wherein the polyalkylene glycol is polyethylene glycol. 6. A support having a laminated structure of two or more layers having at least one polyester layer, curled in the width direction so that the side opposite to the photosensitive layer of the support is concave, and the curl depends on humidity. Silver halide photographic light-sensitive material having a laminated polyester photographic support having properties, at least one photosensitive layer on the convex curl side of the support, and satisfying the following relational expression: material. 5 x (G / D) x (0.5 x H-60) ≤ K (H) ≤ 5 x (G / D)
X (0.35 x H-20) [where H is relative humidity (% RH), K (H) is the degree of curl under the environment of relative humidity H (unit: m ^-1 ), G is silver halide) Total gelatin amount per unit area on the side having the emulsion layer (g / m ² ), D represents the thickness of the support (μm), respectively] 7. A laminated polyester photographic support wherein at least one of the polyester layers is a layer of a modified polyester containing a structural unit having an alkali metal sulfonate group in its side chain in its main chain. Claim 6
The described silver halide photographic light-sensitive material. 8. The silver halide photographic light-sensitive material according to claim 6, wherein the constituent unit having an alkali metal sulfonate group in its side chain is an alkali metal aromatic dicarboxylic acid unit. 9. A laminated polyester in which at least one layer of the polyester layer is a layer of a modified polyester having a constitutional unit having an alkali metal sulfonate group in a side chain and a polyalkylene glycol unit and / or an aliphatic dicarboxylic acid unit in a main chain. 7. The silver halide photographic light-sensitive material according to claim 6, which has a photographic support. 10. The silver halide photographic light-sensitive material according to claim 9, wherein the polyalkylene glycol is polyethylene glycol.