JPH09101591A - Silver halide photographic sensitive material and its support - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material having superior thermal, mechanical, physical, chemical, and optical characteristics, and especially, excellent in optical ones and dimensional stability and small in curling tendency due to winding and superior in operability and handleability by regulating a curling degree to a specified value or lower. SOLUTION: This photosensitive material has a curling tendency of 80m<-1> , preferably, 60m<-1> and it is preferred that a heat absorption amount at a heat absorption peak occurring in a range including the glass transition point (Tg deg.C) of a support is 500-1000mCal/g, especially, 100-600mCal/g. It is obtained by heat treating the support in the temperature range of 40 deg.C-Tg deg.C. The support of this photosensitive material is made of a laminate of >=2 syndiotactic polystyrene sheets and the support is regulated so as to have a curling degree of <=80m<-1> , preferably, <=60m<-1> .

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 support and a silver halide photographic light-sensitive material which are wound into a roll and used.

[0002]

2. Description of the Related Art Conventionally, photographic light-sensitive materials include fibrin-based polymers typified by triacetyl cellulose (hereinafter referred to as "TAC") and polyethylene terephthalate (hereinafter referred to as "P").
On a plastic film support made of a polyester-based polymer typified by "ET").
Being produced by coating a layer of photographic light-sensitive layer.

In general, many photographic light-sensitive materials are used in the form of roll film, and typically, they are stored in a cartridge with a width of 35 mm or less, and are generally loaded into a camera for photographing. Examples thereof include color or black and white negative films used for the above, and black and white photosensitive material films for bright rooms, scanners, facsimiles and the like. TAC is mainly used as the support for the roll film, but the greatest feature is that it has no optical anisotropy and high transparency. Further, another advantage is that it has a very excellent property of decurling after development processing.

That is, the TAC film is characterized by its molecular structure and has a high water absorbing property as a plastic film, and a curl curl developed by being rolled and stored as a roll film is absorbed by water during development processing. Since the chains move and the immobilized molecular chains undergo rearrangement, they are considered to have excellent properties in decurling. As a result, it has an excellent property that the curling curl once formed is eliminated.

On the other hand, in a photographic light-sensitive material using a support having no curling curl eliminating property, when it is used in a roll state, for example, scratches are generated in the printing step, defocusing,
Jamming or the like occurs during transportation, and a jamming phenomenon similarly occurs during transportation of a black-and-white photosensitive material film for a bright room, a scanner, a facsimile, or the like.

On the other hand, the PET film has excellent mechanical properties, dimensional stability and high productivity, and therefore TAC
However, in the roll form widely used as a photographic light-sensitive material, the curling curl strongly remains, so that the handleability after development processing is poor,
Further, the black-and-white photosensitive material film used in a rolled state has poor handleability, and the range of use has been limited while having the above-mentioned excellent properties.

Further, when it is used as a support for a photographic light-sensitive material, it is used at room temperature after being developed and dried.
At this time, a low humidity expansion coefficient is required for a printing photosensitive material application that requires particularly dimensional stability.

Although the PET film does not exhibit elongation due to temperature when used at room temperature, it undergoes a large dimensional change (elongation due to moisture absorption) due to moisture absorption from the liquid development processing solution. In order to suppress the moisture absorption of the support during development and to perform the work within a limited short time after development without hindrance, measures such as applying vinylidene chloride undercoat to both sides of the support have been made. Due to the pollution problem of vinylidene and the like, it is required to develop a support that has a small dimensional change due to moisture absorption even without performing vinylidene chloride subbing.

By the way, the syndiotactic polystyrene (hereinafter referred to as "SPS") support has all the thermal, mechanical, physical, chemical, and optical properties of the PET support, and especially the optical properties. (Light transmittance, haze, etc.), dimensional stability is excellent, and coefficient of hygroscopic expansion is about 1 of PET.
/ 10 or less, which is extremely excellent in dimensional stability under high humidity. Therefore, the SPS support is usefully used in the above-mentioned applications, and is particularly suitable for use as a printing photosensitive material and a print base for ICs, which require dimensional stability.

However, the SPS support, like the PET support, has a strong curling curl in the roll form, and therefore, when used in a roll state in a photographic light-sensitive material, the handleability after development processing is poor, and for example, in the baking step. Causes scratches, defocus, jamming during transport, etc.
In addition, the jamming phenomenon also occurs when a black-and-white photosensitive material film for a bright room, a scanner, a facsimile machine or the like is conveyed.

[0011]

The object of the present invention is to have excellent thermal, mechanical, physical, chemical and optical properties,
In particular, a silver halide photographic light-sensitive material having excellent optical properties (light transmittance, haze, etc.), dimensional stability (small hygroscopic expansion coefficient), little curling curl, and excellent workability and handleability, and its support. To provide.

[0012]

The object of the present invention is attained by adopting one of the following constitutions.

(1) A silver halide photographic light-sensitive material which has at least one silver halide emulsion layer on a syndiotactic polystyrene support and is wound into a roll and has a curl degree of 80 m. ^-1 is a silver halide photographic light-sensitive material of ¹ or less.

(2) The silver halide photographic light-sensitive material as described in (1), which has a curl degree of 60 m ^-1 or less.

(3) A support for the silver halide photographic light-sensitive material according to (1) or (2), wherein the calorific value of an endothermic peak which develops across the glass transition temperature (Tg ° C.) of the support. Is 50 to 1000 mcal / g, and a silver halide photographic light-sensitive material support.

(4) The glass transition temperature (T
The amount of heat of the endothermic peak that develops over a temperature range of 100
The support for a silver halide photographic light-sensitive material as described in (3), which has a density of 600 mcal / g.

(5) The silver halide photographic light-sensitive material as described in (1) or (2), wherein the support is a support in which two or more syndiotactic polystyrene layers different from each other are laminated. .

These problems are related to a silver halide photographic light-sensitive material which has at least one silver halide emulsion layer on a support and is wound into a roll and used. curl degree 80 m ^-1 or less, preferably 60 m ^-1 or less, more preferably heat of an endothermic peak which expresses across a glass transition temperature (Tg ° C.) of the silver halide photographic light-sensitive material support is 50~1000mc
Al / g, preferably 100 to 600 mcal / g, and a silver halide photographic light-sensitive material, or a support for the silver halide photographic light-sensitive material, in which two or more different SPS-based layers are laminated. This is achieved by a silver halide photographic light-sensitive material characterized in that the curl degree of the silver halide photographic light-sensitive material on a support is 80 m ^-1 or less, preferably 60 m ^-1 or less.

The curl degree of the light-sensitive material is preferably as small as possible, and in that sense, the curl degree of 0 m ^-1 is also within the scope of the present invention.

As described above, the support is heat-treated at a temperature of 40 ° C. or higher and a glass transition temperature (Tg ° C.) or lower for 0.1 to 1500 hours before applying the undercoat layer, or after applying the undercoat layer and after coating the emulsion layer. Was achieved by doing. Further, was achieved by a support in which two or more copolymerized SPS-based layers different from each other were laminated.

The above light-sensitive material has a Tg
When the support is heat-treated at a temperature lower than 1, the photosensitive material can be made to have less curl by making it a base with less curl. The same effect as this can be exhibited even if the molecules are slowly cooled from a temperature of Tg or higher at a speed sufficient to reach an equilibrium state in which the free volume is small, and a similar curling effect can be exhibited. .

The support whose free volume is reduced by such heat treatment can be easily quantitatively evaluated by using a differential scanning calorimeter (DSC). It is indicated that the larger the heat absorption amount, the smaller the free volume and the harder the roll is to curl.

By the way, this endothermic peak reflects the heat treatment conditions, and the place of appearance moves. That is, the endothermic peak moves to the higher temperature side as it is heat-treated at a higher temperature. The endothermic peak appearing across Tg is particularly effective, but the endothermic peak appearing in the region exceeding Tg does not work effectively for curling.

The larger the endothermic amount of the endothermic peak that appears across the Tg, the smaller the free volume and the less likely it is to wind, and the endothermic amount in the present invention is 50 to 1000 mcal / g. Preferably there is. More preferably 100 mcal / g or more,
A preferable upper limit is 600 mcal / g. 50 mca
If it is less than 1 / g, it is not possible to obtain the effect of making it difficult for the curl to stick sufficiently. On the other hand, even if it exceeds 1000 mcal / g, the effect of curling will reach a ceiling and it will take a long time.

The above-mentioned light-sensitive material was achieved by using a laminated SPS support characterized by laminating two or more copolymerized SPS-based layers different from each other.

That is, the support is formed by laminating two or more different SPS-based layers, and two or more different SPS-based layers are laminated.
The system layer is a support having different ratios of the copolymerization component to the reaction product. As a copolymerization component other than styrene, the styrene derivative monomer may be contained in an amount of 15 mol% or less, preferably 12 mol% or less.

The laminated SPS-based support has a property of curling on one side of the support surface, although it varies depending on the ratio of the copolymerization component to the reaction product, the type of the copolymerization component, the constitutional thickness, and the number of layers. By utilizing this property, curling curl is attempted to be eliminated (anti-curl is imparted).

Two or more different SPS-based layers are laminated,
The support of the present invention may be laminated in any number of layers, but two or three layers are preferable from the viewpoint of ease of production.

The laminated SPS-based support comprises S constituting each layer.
The type and ratio of the PS copolymerization component may be different, and the thickness of each layer may be different.

To explain the present invention briefly, two-layer and three-layer examples will be described.

In the case of a two-layer laminated SPS-based support, if the laminated thickness is the same, in the case of the same copolymerization component, the layer having a large ratio of the copolymerization component to the reaction product is inwardly curled. In this case, the larger the laminated thickness on the curling side,
Curl is prominently expressed. Further, although the lamination thickness is the same and the ratio of the copolymerization component to the reaction product is the same, in the case of a combination of different types of the copolymerization components, the curling direction differs depending on the combination and cannot be specified. Curl in that direction.

In the case of a two-layer laminated SPS-based support composed of the same copolymerization component, the difference between the two copolymerization components is preferably 5 to 10 mol%. In the case of a combination of different types of copolymerization components, the direction and degree of curl differ depending on the combination and cannot be specified, but similarly a difference of about 5 to 10 mol% may be provided.

In the case of a three-layer laminated SPS-based support, a copolymerized SPS-based layer is laminated on both surfaces of the central SPS-based support. The SPS-based support for the central layer may be the same as or different from the copolymerized SPS on both sides. S on both sides
If the layers constituting the PS-based layer have the same laminated thickness and the same type of copolymerization component, the curl is made with the side having a larger ratio of the copolymerization component to the reaction product as the inside. In this case, the larger the laminated thickness on the curling side, the more remarkable the curling. Further, in the case of a combination in which the types of copolymerization components are different, the curling direction differs depending on the combination and cannot be specified, but curling occurs in either direction.

Three-layer laminate S consisting of the same copolymer component on both sides
In the case of a PS-based support, the difference between the copolymerization components on both sides is preferably 5 to 10 mol% regardless of the SPS-based support of the central layer. In the case of a combination of different types of copolymerization components, the direction and degree of curl differ depending on the combination,
Although it cannot be specified, a difference of about 5 to 10 mol% may be similarly provided.

By utilizing the curling characteristic of the support described above, curling curl generated by storing the light-sensitive material in a direction opposite to the curling direction can be canceled to obtain a flat photograph. It is intended to obtain a light-sensitive material.

The present invention will be described in more detail below. First, the syndiotactic polystyrene of the present invention will be described.

In the present invention, a film containing syndiotactic polystyrene (SPS) as a main component means that the stereoregular structure (tacticity) is mainly a syndiotactic structure, that is, a main chain formed from carbon-carbon bonds. On the other hand, a phenyl group or a substituted phenyl group, which is a side chain, has a three-dimensional structure in which they are alternately located in opposite directions,
The main chain of the main chain is a styrene-based polymer which is a racemo chain or a composition containing the same. If it is a styrene homopolymer, it can be polymerized by the method described in JP-A-62-117708. For other polymers, JP-A-1-46912 and 1-178505.
It can be obtained by polymerization according to the method described in No.

The tacticity is quantified by a nuclear magnetic resonance method (13C-NMR method) using isotope carbon. The tacticity measured by 13 C-NMR method is the existence ratio of a plurality of continuous structural units, for example, 2
In the case of styrene-based polymer having a syndiotactic structure, the styrene-based polymer mainly having a syndiotactic structure can be represented by a diad in the case of three, a triad in the case of three, and a pentad in the case of five. % Or more, preferably 85% or more, or racemic triad 60% or more, preferably 75% or more, or racemic pentad 30% or more, preferably 50% or more.

Specific monomers of the polymer constituting the syndiotactic polystyrene composition include alkylstyrene such as styrene and methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, and the like. It is a single or a mixture containing vinyl benzoate as a main component.

At the above-mentioned temperature of 40 to Tg (° C.),
When the heat treatment is performed for (0.1 to 1500) hours, the SPS-based polymer to be used may be a copolymerized SPS-based support as long as the basic characteristics of the SPS-based support are not lost.
On the other hand, in the case of the SPS-based laminated support, it is intended to impart the anti-curl property to the support itself without heat treatment, and it is a reaction product of a copolymerization component between two layers of the laminated SPS-based support. The difference in the ratio to
It is good to be mol%, preferably 5 to 10 mol%. If the difference in the ratio of the copolymerization component between the two layers to the reaction product is 3 mol% or more, the curl degree is 80 m ^-1 or less,
If it is 5 mol% or more, 60 m ^-1 or less can be achieved.

The polystyrene resin having a syndiotactic structure of the present invention contains the above raw material monomers
As a polymerization catalyst, those containing (a) a transition metal compound and (b) an aluminoxane as main components described in JP-A-5-320448, pages 4 to 10, or (b).
It can be produced by polymerization using a compound containing as a main component a compound capable of reacting with (a) a transition metal compound and (c) a transition metal compound to form an ionic complex.

To produce the styrenic polymer used in the film of the present invention, the styrenic monomer is first sufficiently purified and then polymerized in the presence of any of the above catalysts. At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent, etc. may be appropriately selected. Usually from -50
At a temperature of 200 ° C, preferably 30-100 ° C,
Polymerization is carried out for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in the solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane may be used alone or in combination. It can be used in combination. in this case,
The monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like.

The molecular weight of the SPS film of the present invention is not limited as long as it is formed, but the weight average molecular weight is preferably 10,000 to 3,000,000, and particularly preferably 30,000 to. It is preferably 1,500,000. The molecular weight distribution (weight average molecular weight / number average molecular weight) at this time is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights. In addition, other monomers copolymerizable with these may be copolymerized to the extent that the effects of the present invention are not impaired.

Specific examples of polymerization of SPS used in the present invention are shown below, but the present invention is not limited thereto.

SPS according to Japanese Patent Laid-Open No. 3-131843
Pellets were made. From the catalyst adjustment to the polymerization reaction,
All were carried out under a stream of dry argon. Copper sulfate pentahydrate (CuSO4.5H2O) in a glass container with an internal volume of 500 ml
Add 17.8 g (71 mmol) of purified benzene (200 ml) and trimethylaluminum (24 ml) and stir at 40 ° C for 8 hours.
The catalyst was adjusted by stirring for a time. This was placed under an argon gas flow. After filtering through 3 glass filters, the filtrate was freeze-dried. This was taken out, put in a 2 l stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein and heated to 90 ° C. 1 liter of purified styrene was put in this, and the polymerization reaction was continued at this temperature for 8 hours. After that, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added with stirring to deactivate the catalyst. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried. This was pelletized with an extruder and then dried at 130 ° C.

The SPS-based monolayer support used for the heat treatment of the present invention is preferably SPS alone made from styrene, but as a film further containing SPS,
By mixing SPS with a styrene-based polymer (IPS) having an isotactic structure in which the main chain is a meso chain, the crystallization rate can be controlled and a stronger film can be obtained. When SPS and IPS are mixed, the ratio depends on the stereoregularity of each other, but 30:70 to 99: 1, preferably 5
It is 0:50 to 98: 2.

SPS used for imparting anti-curl of the present invention
As the monomer to be copolymerized with the base laminated support, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene, chlorostyrene, alkoxystyrene, vinyl benzoate, etc. are mainly used for the basic styrene skeleton. The ingredients may be used alone or in a mixture.

The support may contain inorganic fine particles, antioxidants, UV absorbers, antistatic agents, dyes, pigments, dyes, etc., for the purpose of imparting functionality, within a range not impairing the object of the present invention. Is possible.

The polymer used for forming SPS has a weight average molecular weight of 10,000 or more, more preferably 30,
It is more than 000. When the weight average molecular weight is less than 10,000, a film excellent in strength characteristics and heat resistance cannot be obtained. The upper limit of the weight average molecular weight is not particularly limited, but if the weight average molecular weight is 1,500,000 or more, rupture may occur due to an increase in stretching tension, which is not preferable. Furthermore, the SPS film of the present invention is
The SPS-based pellets are dried at 120 to 180 ° C. for 1 to 24 hours under vacuum or normal pressure under an atmosphere of inert gas such as air or nitrogen. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis.
Hereafter, 0.005% or less is more preferable. However, these methods are not particularly limited as long as the purpose is achieved.

A known method can be applied to the extrusion during film formation. For example, it is preferable to extrude the SPS type single layer support with a T die. The SPS-based laminated support is preferably extruded with a laminated T die. 2 SPS pellets
It is melted and extruded at 80 to 350 ° C., and is cooled and solidified on a casting roll while electrostatically applied to produce an unstretched film.

Next, this unstretched film was biaxially stretched to obtain 2
Orient the axis. As a stretching method, a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are sequentially performed, a sequential biaxial stretching method of transverse stretching / longitudinal stretching, a transverse / longitudinal / longitudinal stretching method, a longitudinal / transverse stretching method.・ Longitudinal stretching method, longitudinal / longitudinal / horizontal stretching method, or simultaneous 2
An axial stretching method or the like can be adopted and can be appropriately selected according to various characteristics such as required mechanical strength and dimensional stability. In general, a sequential biaxial stretching method in which stretching is first performed in the longitudinal direction and then in the width direction is preferable, and in this case, the stretching ratio in the longitudinal and transverse directions is 1.5 to 6 times, and the longitudinal stretching temperature is
Although it depends on the glass transition temperature (Tg) of the polymer, it is usually stretched in the temperature range of (Tg + 10) ° C. to (Tg + 50) ° C. In the case of an SPS type film, it is preferably carried out at 110 to 150 ° C. The stretching temperature in the width direction is preferably slightly higher than that in the longitudinal direction and is preferably 115 to 160 ° C.

Next, this stretched film is heat-treated.
The heat treatment temperature in this case can be appropriately changed depending on the application. 1 for shrink wrapping applications that require high shrinkage
For photography, printing, and medical applications requiring dimensional stability of 15 ° C or higher and 175 ° C or lower, 175 to 2 is appropriately used depending on the purpose.
A temperature of 70 ° C is adopted. The heat treatment time is not particularly limited, but is usually 3 seconds to 100 seconds. It goes without saying that vertical heat relaxation, horizontal heat relaxation treatment and the like may be performed as necessary.

After this, the film may be rapidly cooled and wound, but it is 0.1 minute to 1500 at a temperature between Tg and the heat treatment temperature.
Slowly cool over time, and wind it around a large diameter core 40 ℃ ～ T
It is preferable to further cool at an average cooling rate of −0.01 to −40 ° C./min between g ° C., since it has an effect of making it difficult to curl the support. Of course, the heat treatment between 40 ° C. and Tg ° C. is carried out for 0.1 to 10 minutes after the support is wound and after the emulsion is coated.
It may be put in a constant temperature bath for 1500 hours.

Therefore, the heat treatment may be performed at a temperature of Tg or lower, may be performed at a constant temperature of Tg or lower, or may be performed while slowly cooling from Tg. Due to such heat treatment, the free volume is reduced, and an endothermic peak appears at a position beyond Tg as described above. This heat treatment is 40
It may be performed at a temperature of not lower than Tg and not higher than Tg, or may be gradually cooled from a temperature not lower than Tg to a temperature lower than Tg. If the temperature is lower than 40 ° C, it takes too much time to obtain the target curling improvement effect. If the heat treatment temperature is too close to Tg, the film flatness is lost. The heat treatment temperature is preferably 55 ° C or higher and (Tg-10) ° C or lower. The heat treatment time is preferably 0.1 hour or more and 1500 hours or less. The heat treatment for 0.1 hour or less has no curling improvement effect, while the effect saturates for 1500 hours or more. At a heat treatment temperature of 55 ° C or higher and (Tg-10) ° C or lower, the heat treatment time is preferably 2 to 200 hours.

If the heat treatment time is long, the productivity is lowered, which is not preferable. The heat treatment temperature is set to a relatively high value that does not affect quality, and short-time treatment is preferable.

When the heat treatment is performed at this constant temperature, the following method can be considered. That is, it is a method in which the support is rolled and placed in a constant temperature bath and heated. According to this method, it takes a long time to raise the temperature from room temperature to a predetermined temperature for a long support having a length of 1000 m or more and a wide support having a width of 1000 mm or more. In order to drastically reduce this time, it is possible to employ means such as holding the support on a heat roll so that the support has a predetermined temperature during conveyance, or blowing hot air to wind the support while it is not cooled.

In the method of heat treatment while slowly cooling, the temperature is once raised to Tg or higher and then Tg is maintained.
Gradually cool to the following temperature. This heat treatment may be performed in a dry state, a humidified state, or the like, and is not particularly limited to these methods.

Further, such heat treatment can be carried out immediately after film formation on the SPS support. It is also possible to carry out after the surface treatment step (corona treatment, glow discharge treatment, etc.) as a measure for improving the adhesion between the undercoat layer and the support. It is also possible to carry out after coating the undercoat layer or after coating the emulsion layer. The method of improving the curl due to heat treatment loses its effect when exposed to a temperature of Tg or higher, so it is necessary to take measures only for the temperature of Tg or higher. At the same time, it is fatal for a photographic light-sensitive material that a blocking phenomenon occurs or the emulsion layer deteriorates by performing heat treatment, and measures such as setting the heat treatment temperature as low as possible are taken. You must avoid it.
The heat treatment temperature is 40 ° C. or higher and Tg ° C. or lower. Although the Tg of the SPS support changes depending on the ratio of the copolymerization component,
Essentially SPS homopolymer support and mechanical, physical,
No significant difference in chemical properties was found, but the Tg of the SPS support containing some copolymerization components was 95-100.
It is about ° C. Therefore, the temperature when the heat treatment for reducing the winding around the SPS support itself is carried out is 40 ° C.
It is preferably Tg or lower, in other words, 95 to 100 ° C. or lower. When heat-treating after the subbing treatment, 70 ° C. or lower and 40 ° C. or higher are preferable from the viewpoint of avoiding the blocking phenomenon.
Similarly, when heat-treating after coating the emulsion, 70 ° C or lower 40
C. or higher is preferred.

Glass transition temperature (Tg ° C.) in the present invention
Using a differential scanning calorimeter (DSC), when the temperature of 10 mg of the sample film was raised at 20 ° C./min in a nitrogen stream, the temperature that started to deviate from the baseline and the temperature that returned to the new baseline were measured. Defined as the arithmetic mean. However, when an endothermic peak appears, the temperature showing the maximum value of this endothermic peak is defined as Tg. The SPS of the present invention has a Tg
Is about 100 ° C., but its Tg decreases depending on the type and ratio of the SPS copolymerization component. Moreover, since the dimensional stability inherent in SPS is impaired by the increase in the amount of copolymerization components, SP
The range that does not impair the original properties of S, that is, the copolymerization component is 15
It is preferably at most mol%, more preferably at most 12 mol%. S
Considering storage in a warehouse, transportation by freight cars, and automobiles, the atmosphere to which the PS-based support is exposed is heated to about 80 ° C. by direct sunlight from the automobiles during automobile transportation. Therefore, the Tg of the support of the present invention is preferably 80 ° C. or higher. However, the usage conditions differ depending on the application, and are not limited to these numerical values.

On the other hand, the method for producing an SPS-based laminated support for imparting anti-curl properties and eliminating curl quirks caused by winding on a core is carried out by an SPS-based polymer having different copolymerization components regardless of heat treatment. Are laminated in a molten state in a laminar flow, and then extruded from a die, or cooled or solidified SPS-based unstretched support or SPS-based uniaxially stretched support having different copolymerization components or the same copolymerization component. It is obtained by extrusion laminating molten SPS polymers of different amounts, then stretching in both longitudinal and transverse directions, or in the direction perpendicular to the uniaxial stretching direction and heat setting. Extrusion conditions, stretching temperature, stretching ratio, heat setting temperature, etc. of the SPS polymer are SP
Although it depends on the combination of the S-based laminated supports, it may be adjusted to select the optimum conditions. Of course, the lamination consists of a combination of two or more layers, with different copolymer components and different amounts of SP.
It is composed of a combination of S-based polymers.

In addition to the above, surface treatment (giving a gas barrier property by applying vinylidene chloride, imparting slipperiness, adhering property by in-line application, etc.) may be performed by the same method. That is, it can be produced by in-line coating on an SPS-based single-layer or laminated unstretched support, or after uniaxial stretching of the SPS-based support, or after biaxial stretching of the SPS-support.

The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

The thickness of the thus-obtained syndiotactic polystyrene-based stretched support varies depending on the use of the photographic light-sensitive material, but is 60 to 122 μm for color light-sensitive materials.
m, 100 μm for medical and printing materials, 175 for X ray
μm thickness and a wide range, but the above film forming conditions are 50 to
It is effective for a thickness of 250 μm.

Next, the subbing treatment of the support before coating the hydrophilic colloid layer for silver halide photographic light-sensitive materials will be described. When applying the undercoat layer, chemical treatment, mechanical roughening treatment,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
It is preferable to perform glow discharge treatment, active plasma treatment, laser treatment and the like. The surface tension of the surface is preferably 50 dyne / cm or more by these treatments. As the subbing layer, any of those used in the art may be used. The subbing layer may be a single layer, but it is preferably a multi-layer in order to obtain more functionality and enhance the adhesive strength.

The subbing layer method will be described below. In the multi-layer method, the first subbing layer preferably adheres well to the support, and the materials include unsaturated carboxylic acids such as methacrylic acid and acrylic acid, or esters thereof, styrene, vinylidene chloride, vinyl chloride, Polymers or copolymers obtained from the above monomers, water-dispersible polyesters, polyurethanes, polyethyleneimines, epoxy resins, and the like. Of these, preferred are copolymers having a water-dispersible polyester and a styrene polymer as constituent elements. The copolymer or composition containing the water-dispersible polyester and the styrene polymer as constituent elements will be described.

The water-dispersible polyester is a substantially linear polymer obtained by a polycondensation reaction between a polybasic acid or its ester-forming derivative and a polyol or its ester-forming derivative. Polybasic acid components of this polymer include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-
Examples thereof include cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid and the like. Unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and p
A small proportion of hydroxycarboxylic acids such as -hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used.

Further, as the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, triglyceride and triethylene glycol are used. Methylolpropane, poly (ethylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol.

In order to impart water dispersibility and water solubility to the water-dispersible polyester, introduction of a sulfonate, diethylene glycol, polyalkylene ether glycol or the like is an effective means. In particular, it is preferable that the dicarboxylic acid component having a sulfonate (dicarboxylic acid having a sulfonate and / or its ester-forming derivative) is contained in an amount of 5 to 15 mol% with respect to the total dicarboxylic acid component in the water-dispersible polyester. .

As the dicarboxylic acid having a sulfonic acid salt and / or its ester-forming derivative used in the undercoat layer of the present invention, one having a group of an alkali metal sulfonic acid salt is particularly preferable, for example, 4-sulfoisophthalic acid, 5
-Alkali metal salts such as sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid or ester-forming derivatives thereof are used. However, 5-sulfoisophthalic acid sodium salt or its ester-forming derivative is particularly preferable. The dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is particularly preferably used in an amount of from 6 to 10 mol% based on all dicarboxylic acid components from the viewpoint of water solubility and water resistance.

As the monomer of the styrene polymer used in the undercoat layer of the present invention, when styrene is used alone or when it is copolymerized, for example, alkyl acrylate, alkyl methacrylate (wherein the alkyl group is a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxyethyl acrylate, 2-hydroxy Hydroxy-containing monomers such as ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylolmethacrylamide, N-methylo. Le acrylamide, N, N-
Amido group-containing monomers such as dimethylolacrylamide and N-methoxymethylacrylamide; amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminomethacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; acrylic acid Monomers containing carboxyl groups such as methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof; styrenesulfonic acid, vinylsulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt) Monomers containing sulfonic acid groups or salts thereof such as; carboxylic acid groups such as itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt, ammonium salt) or salts thereof Mar; maleic acid, monomers containing an acid anhydride such as itaconic anhydride; vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, vinyl chloride, vinyl acetate, vinylidene chloride and the like. The above-mentioned monomers can be copolymerized by using one kind or two or more kinds. To modify the water-dispersible polyester into a vinyl-based polymer, a method of introducing an addition-polymerizable group at the terminal of the water-dispersible polyester and copolymerizing with a monomer of the vinyl-based copolymer for grafting, There is a method of introducing a reactive group at the time of polycondensation of a water-dispersible polyester such as a carboxylic acid, a glycidyl group or an amino group as a monomer by polymerizing a system copolymer. The polymerization initiator includes ammonium persulfate, potassium persulfate, sodium persulfate and the like, and ammonium persulfate is preferably used.

Further, regarding polymerization, a soap is not particularly required, and the reaction can be carried out soap-free. But,
For the purpose of improving polymerization stability, a surfactant can be used as an emulsifier in the system, and a general nonionic or anionic surfactant can be used.

The ratio of modification of the above water-dispersible polyester and styrene copolymer is 99/1 to 5/95, preferably 97/3 to 50/50, and more preferably 95/5.
~ 80/20 is good.

In order to improve the coatability, it is preferable to add an activator or a cellulose compound such as methylcellulose to the first subbing layer.

The subbing treatment may be carried out after the film formation, but if the subbing composition can be stretched, before the longitudinal stretching which is in the midst of the film formation, between the longitudinal stretching and the transverse stretching, It can be performed at any place such as after transverse stretching and before heat treatment.
When stretching is not possible For example, when a polymer having a hydrophilic group is used, it may not be possible to stretch due to strong interaction between hydrophilic polymers, but stretching under steam, polyglycerin as a stretching aid, etc. It becomes possible to stretch by adding.

Preferred among the monomers having a hydrophilic group are unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride. From the viewpoint of water resistance, the content is preferably 1 to 10% by weight,
More preferably 1 to 8% by weight, more preferably 1 to 6
%, Most preferably 1 to 4% by weight. Further, as the fourth component of this copolymer, other copolymerizable monomers may be copolymerized in the range of 0 to 15% by weight, preferably 0 to 10% by weight, if necessary. Examples of this include alkyl-substituted styrenes such as methylstyrene,
Chlorostyrene, chloromethyl styrene and other halogenated styrenes, acrylonitrile and other unsaturated nitrile compounds, methyl acrylate, methyl methacrylate, t-butyl acrylate and other aliphatic compounds, cyclohexyl methacrylate and other alicyclic compounds, and benzyl acrylate. And aromatic (meth) acrylic acid ester compounds, such as butadiene and isoprene, which are rubber-modified compounds.

The method for producing these copolymers is not particularly limited, and can be usually obtained by radical polymerization using a generally known radical initiator.

GP of a copolymer composed of these monomers
The weight average molecular weight in terms of standard polystyrene measured by the C method is preferably 1500 to 700,000, and more preferably 2000 to 500000.

The second subbing layer is preferably a hydrophilic resin layer which adheres well to the photographic emulsion layer. As a binder that constitutes the hydrophilic resin layer, gelatin, a gelatin derivative,
Casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, water-soluble polymers such as hydroxyethyl cellulose, a combination of polystyrene sulfonic acid soda copolymer and hydrophobic latex, and the like, Gelatin is preferred.

A hardener is preferably used in the second undercoat layer to increase the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, and US Pat. , 732, 303
No. 3,288,775, British Patent 974,723.
No. 1,167,207, etc., compounds having a reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl)
Urea, 2-hydroxy-4,6-dichloro-1,3,5
-Triazine, divinyl sulfone, 5-acetyl-1,
3-Diacryloylhexahydro-1,3,5-triazine, U.S. Pat. Nos. 3,232,763 and 3,635.
718, compounds having reactive olefins described in British Patent 994,809, etc., US Pat. No. 3,539,64
No. 4, No. 3,642, 486, Japanese Patent Publication No. 49-1356
No. 8, No. 53-47271, No. 56-48860,
JP-A-53-57257, JP-A-61-128240,
No. 62-4275, No. 63-53541, No. 63-
Vinylsulfone compounds described in No. 264572, N-
Hydroxymethylphthalimide, US Patent 2,732
No. 316, 2,586,168, etc., N-methylol compounds, US Pat. No. 3,103,437, etc., isocyanate compounds, US Pat. No. 2,983,611.
And the aziridine compounds described in U.S. Pat. Nos. 2,725,294 and 2,725,2.
Acid derivatives described in US Pat. No. 3,100,7
No. 04, etc., carbodiimide compounds, U.S. Pat. No. 3,091,537, etc. epoxy compounds, U.S. Pat. Nos. 3,321,313, 3,543,292, etc. isoxazole compounds. , Organic hardeners such as halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-59625 and JP-A-62-26 are mentioned.
No. 2854, No. 62-264044, No. 63-184.
No. 741 N-carbamoylpyridinium salts,
It has two or more acyl-imidazoles described in JP-B-55-38655, N-acyloxyimidazoles described in JP-B-53-22089, and two or more N-acyloxyimino groups described in JP-B-53-22089. Compounds, compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113
A compound having a phosphorus-halogen bond described in No. 929,
JP-A-60-225148 and 61-240236.
Nos. 63-41580 and chloroformamidinium compounds are known.

The second subbing layer preferably contains, as a slip agent, inorganic fine particles such as silicon dioxide and titanium oxide, and an organic matting material (1 to 10 μm) such as polymethylmethacrylate. In addition to these, various additives such as an antistatic agent, an antihalation agent, a coloring dye, a pigment, and a coating aid may be contained, if necessary.

Among these, it is preferable to include an antistatic agent. Preferred antistatic agents include non-photosensitive conductors and / or semiconductor fine particles.

The non-photosensitive conductor and / or semiconductor fine particles used in the undercoat layer of the present invention are electrically conductive due to charge carriers such as cations, anions, electrons and holes present in the particles. As shown, it may be an organic material, an inorganic material, or a composite material of both. It is preferably a compound having electron conductivity, and examples of organic materials include polymer fine particles such as polyaniline, polypyrrole, and polyacetylene. Examples of inorganic materials include fine particles of metal oxides that easily form nonstoichiometric compounds such as oxygen-deficient oxides, metal-excess oxides, metal-deficient oxides, and oxygen-excess oxides. If it is a charge transfer complex or an organic-inorganic composite material, a phosphazene metal complex or the like can be mentioned. Among these, the most preferable compound for the undercoat layer of the present invention is metal oxide fine particles which can be manufactured by various methods. Further, the conductor in the undercoat layer of the present invention has a volume resistivity of 10 ³ Ω · cm or less, and the semiconductor has a volume resistivity of 10 ¹² Ω · cm or less as a conductor and a semiconductor, respectively.

A preferred method for producing conductive fine particles will be illustrated below.

<Preparation of Semiconductor Fine Particle Solution> 65 g of stannic chloride hydrate was dissolved in 2000 cc of a water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The formed precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate was dropped into distilled water after washing the precipitate, and after confirming that there was no reaction of chlorine ions, 1000 cc of distilled water was added to bring the total amount to 20.
00cc. Further, 40 cc of 30% ammonia water was added and heated in a water bath to obtain a colloidal gel dispersion.

<Preparation of Semiconductor Fine Particle Powder> 65 g of stannic chloride hydrate and 1.5 g of antimony trichloride were dissolved in 1000 g of ethanol to obtain a uniform solution. 1N- in this solution
A sodium hydroxide aqueous solution was added dropwise 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 to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated three times to remove excess ions.
100 g of colloidal precipitate from which excess ions were removed was added with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water.
Was sprayed into a firing furnace heated to 900 ° C. to obtain a powder mixture of stannic oxide and barium sulfate having a bluish average particle size of 0.1 μm.

The coating liquid concentration of the undercoat layer composition is usually 20% by weight or less, preferably 15% by weight or less. The coating amount is 1 to 30 g by weight of the coating liquid per 1 m ² of the film.
More preferably, it is 5 to 20 g.

As a coating method, various known methods can be applied. For example, a roll coating method, a gravure roll coating method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method, a curtain coating method and the like can be applied alone or in combination.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material according to the present invention is preferably subjected to photographic processing after exposure by an automatic processor having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

As the developing solution used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (e.g., hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4-)
Methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone, etc.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-
o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA)
Iron salt, DTPA nickel salt, etc.) can be used alone or in combination. Among them, it is preferable to use a developer containing ascorbic acid and its derivative. Ascorbic acid and its derivatives are known as developing agents and are disclosed in, for example, US Pat. No. 2,688,548.
No. 2,688,549, 3,022,168,
3,512,981, 4,975,354 and 5,
Those described in the specification of No. 326,816 can be used.

Further, a developing agent for ascorbic acid and its derivatives and 3-pyrazolidones (for example, 1-phenyl-3
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3 -Pyrazolidone)
And aminophenols (eg o-aminophenol,
p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) and dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone monosulfonate, hydroquinone mono). Sodium sulfonate, 2,
It is preferable to use a developing agent such as 5-hydroquinone disulfonic acid potassium salt) in combination. When used in combination, the developing agent for 3-pyrazolidones, aminophenols and dihydroxybenzenes substituted with a hydrophilic group is usually used in an amount of 0.01 or more and less than 0.2 mol per liter of the developing solution. Is preferred. In particular, a combination of ascorbic acid and its derivative with 3-pyrazolidones, and a combination of ascorbic acid and its derivative with 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

An alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) are added to the developer. Preferably. As the pH buffering agent, carbonate is preferable, and the addition amount thereof is preferably 0.5 mol or more and 2.5 mol or less, and more preferably 0.75 mol or more and 1.5 mol or less, per liter. If necessary, a solubilizing agent (for example, polyethylene glycols, their esters, alkanolamines, etc.), a sensitizer (for example, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example ethylenediamine tetrachloride). Acetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc., development accelerators (eg US Pat. No. 2,304,025)
, A compound described in JP-B-47-45541), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, the pH is 8.5 or more 1
It is 0.4 or less.

As the fixing liquid, those having a generally used composition can be used. The fixing solution generally has a pH of 3-8. As a fixing agent, sodium thiosulfate,
Potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixing solution contains a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates capable of softening water. Compounds such as agents may be included.

After the fixing treatment, it is washed with water and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide,
Ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. are used in combination, aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid) Or an alkali metal salt thereof,
Nitrilotriacetate, polyphosphate, etc.), anti-binders (for example, phenol, 4-chlorophenol, cresol, O-
Phenylphenol, chlorophene, dichlorophene,
Formaldehyde, P-hydroxybenzoic acid ester,
2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxy Diphenyl ether, etc.), a color tone adjuster and / or a residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
-Sodium mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.) Is contained. Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

In order to shorten the developing time, the total processing time (Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when processing using the automatic developing machine
to Dry) is preferably 60 seconds or less and 10 seconds or more.

The halogen composition of silver halide in the silver halide emulsion is not particularly limited, but in the case of processing with a small replenishment amount or rapid processing, silver chloride, 60 mol%
It is preferable to use a silver halide emulsion having the above composition of silver chlorobromide containing silver chloride and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of the silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, many compounds known as antifoggants or stabilizers such as azoles, mercaptopyrimidines, mercaptotriazines, azaindenes, benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic acid amide can be added. .

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

An inorganic or organic hardener is added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer as a crosslinking agent for the hydrophilic colloid such as gelatin. These hardeners are available from Research Disclosure (Research D
(Isclosure) 176, 17643 (published December 1978), page 26, paragraphs A to C.

Various other additives are used in the light-sensitive material. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

Regarding the above-mentioned additives and other known additives, for example, Research Disclosure No.
No. 17643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989).

The light-sensitive material of the present invention is used for radiography.
It can be used for various purposes such as printing plate making, general photography such as color or black and white negative film, and direct viewing.

[0110]

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

[1] Evaluation Method First, the curling curl, the glass transition temperature measuring method, the endothermic peak calorimeter measuring method and the like will be described.

(1) Roll curl The curl curl indicates the curl in the winding direction when the curl is wound around the core. The sample size of the silver halide photographic light-sensitive material film is 12 cm long (longitudinal direction during manufacturing).
A film as a sample having a width of 35 mm (horizontal direction at the time of production) was conditioned under a condition of 23 ° C. and 55% RH for 1 day, and then the film was lengthened to a core having a diameter of 10.8 mm. Winding in the vertical direction (vertical direction during manufacturing), 55 ° C, 20% RH
Heat treatment was performed for 4 hours under the atmosphere. afterwards,
After allowing to cool in an atmosphere of 23 ° C. and 55% RH for 30 minutes, the core is released, and after 1 minute, the curl curl degree of the film is measured.

The curling curl test conditions described above are set so that the inner diameter of the photosensitive material for printing is usually 2 to 3
It corresponds almost to the state after being stored for 2 years when wound on an inch core.

The curl degree of curling is represented by 1 / R (m ^-1 ). This R represents the radius of curvature of the curled film,
The unit is m (meter).

(2) Glass transition temperature (Tg) Using a differential scanning calorimeter (DSC), sample film 1
When 0 mg was heated at 20 ° C / min in a nitrogen stream,
It is defined as the arithmetic mean temperature (° C) of the temperature that starts to shift from the baseline and the temperature that returns to the new baseline. However, when an endothermic peak appears, the temperature showing the maximum value of this endothermic peak is defined as Tg (° C.).

(3) Endothermic peak calorimetric method In the DSC measurement of (2) above, the endothermic peak expressed across the Tg, which is surrounded by a line connecting the temperature at which the baseline starts to shift and the temperature at which the baseline returns to the new baseline. The amount of heat (unit: mcal / g) is calculated from the area of. The Tg of the SPS-based film exists between 90 and 100 ° C.

As the sample film, an SPS support film in which the undercoat layer and the emulsion layer were peeled off from the product film was used.

(4) Workability evaluation method Heat treatment (55 ° C., 20% R) by the method described in (1) above.
(H, 4 hours) A sample was continuously cut out from a product roll wound around a core having an inner diameter of 3 inches and used for a printing plate making scanner, and the workability was evaluated as follows. Note that this condition was adopted as being equivalent to the accelerated test when left at room temperature for 2 years.

A) There is no jamming, and the cut sheet cut out is flat, and there is no problem in workability; ◎ b) There is no jamming, but the cut sheet cut out is curled weakly However, there is no problem in workability; ○ c) There is a lot of jamming, the curl of the cut sheet cut out is severe, and workability is very problematic;
× (5) Flatness evaluation method The flatness of the finished product was evaluated according to the following criteria while irradiating a cut sheet cut from a roll with a light beam obliquely.

A) The product film is flat and has no irregularities; ◎ b) The product film appears to be slightly undulating, but practically harmless; ○ c) The product film is irregular. ΔD) Blocking phenomenon occurred at the stage of coating the subbing layer and heat treatment, and the emulsion layer could barely be coated, but could not be used as a product at all. × (6) Comprehensive evaluation The finished products were comprehensively evaluated according to the following criteria.

A) A product film that is excellent in all respects without problems; ◎ b) A product film that leaves room for improvement in appearance but has no problem in practical use as a whole; ○ c ) Comprehensively, there is a problem in practical use and cannot be used; × Preparation of support [2] Preparation of sample (1) Polymerization of SPS 100 parts by weight of styrene, 56 g of triisobutylaluminum in 200 parts by weight of toluene Using 234 g of pentamethylcyclopentadienyl titanium trimethoxy, a reaction was carried out at 96 ° C. for 8 hours. After decomposing and removing the catalyst with a methanol solution of sodium hydroxide, the catalyst was washed 3 times with methanol to give SPS having a weight average molecular weight of 280,000.
34 parts by weight of polymer were obtained.

(2) Preparation of SPS film The obtained SPS polymer pellets were heated at 150 ° C. for 3 hours,
Dry under nitrogen atmosphere, melt extrude into film form from T-die at 330 ° C., and apply sheet by electrostatic application method to 4
An unstretched film was prepared by rapidly cooling and solidifying on a cooling drum at 0 ° C., and the thickness was 1050 μm and 1370, respectively.
μm and 1850 μm of unstretched film were obtained, and the unstretched film was stretched at 135 ° C. in the longitudinal direction by 3.1 times, then at 140 ° C. in the transverse direction by 3.4 times, and at 250 ° C. at 1 ° C.
After heat setting for 5 seconds, the thickness is 100 μm, 130 respectively
A biaxially oriented SPS film of μm and 175 μm was wound to obtain an SPS roll film (support A) (the roll films are designated as A-1, -2 and -3, respectively). The glass transition temperature Tg of the obtained roll film (A-1 to A-3) was 95 ° C.

[3] Experiment-1 Treatment of Support Films Examples 1 to 11 and Comparative Examples 1 to 3 (Table 1) The biaxially oriented SPS roll films of Supports A-1 to A-3 were 85 After heat treatment at 48 ° C. for 48 hours, surface treatment, undercoat layer coating, and silver halide emulsion coating were carried out as described below to obtain the product roll films of Examples 1 to 3 in order.

Examples 4 to 7 and Comparative Examples 1 to 3 shown below
In both cases, the biaxially oriented SPS roll film was heat-treated in the same manner as described above, followed by surface treatment, undercoat layer coating, and silver halide emulsion coating in the order described below. It is a product roll film.

The biaxially oriented SPS roll film of the support A-1 was heat-treated at 40 ° C., 55 ° C., 85 ° C. and 95 ° C. for 48 hours to obtain films of Examples 4 to 7 in order.

Example 4 (A-1 support at 48 ° C. at 48 ° C.
Comparative Examples 1 and 2 are those in which the heat treatment temperature of the heat treated for a time) was changed to 35 and 100 ° C.

Example 6 (A-1 support at 48 ° C. at 48 ° C.
Heat treatment time of 0.1, 2, 2
What changed to 00, 1500 hours is shown in Examples 8-11. A comparative example 3 in which the heat treatment time was changed to 0.05 hours is also shown.

(1) Surface Treatment Both surfaces of the SPS film having a contact angle of 90 ° of A-1 to A-3 were
A corona discharge treatment was performed at a corona discharge voltage of 80 Watt / m ² to obtain a film having a contact angle of 40 °.

(2) Undercoating of SPS film and coating of silver halide photographic light-sensitive layer On one undercoating layer of the above-mentioned support, a gelatin subbing layer of the following Formulation 1 was used in which the amount of gelatin was 0.5 g / such that m ^2, amount of silver 1 silver halide emulsion layer 1 formulation 2 thereon.
5 g / m ² , the amount of gelatin is 0.5 g / m ² , and a coating solution of the following formulation 3 as an intermediate protective layer is further formed on the upper layer so that the amount of gelatin is 0.3 g / m ² and the upper layer. The silver halide emulsion layer 2 of Formula 4 was added in an amount of 1.4 g / g
Simultaneous multilayer coating was performed so that the amount of m ² and the amount of gelatin were 0.4 g / m ^{2 and} that the coating solution of the following formulation 5 was 0.6 g / m ² . On the opposite subbing layer, a backing layer of the following formulation 6 was prepared so that the amount of gelatin would be 0.6 g / m ^2, and a hydrophobic polymer layer of the following formulation 7 was further formed thereon, and the following formulation was also prepared thereon. A sample was obtained by simultaneously coating the backing protective layer of No. 8 with the emulsion layer side so that the amount of gelatin was 0.4 g / m ² .

Formulation 1 (gelatin subbing layer composition) Gelatin 0.5 g / m ² Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A described later A silver amount of 1.5 g / m ² Solid dispersion fine particles of dye AD-8 (average particle size 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / M ² Hydrazine derivative H-7 20 mg / m ² Redox compound: RE-1 20 mg / m ² Compound e 100 mg / m ² Latex polymer f 0.5 g / m ² Hardener g 5 mg / m ² S- 1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² formulation 3 (interlayer composition) gelatin 0.3 g / m ² S-1 2 mg / m ² Formulation 4 (composition of silver halide emulsion layer 2) Silver halide emulsion B described later so that the amount of silver was 1.4 g / m ² Sensitizing dye d-1 was increased by 3 mg / m ^2. Sensitizer d-2 3 mg / m ² Hydrazine derivative H-20 20 mg / m ² Nucleation accelerator: Exemplified compound Nb-12 40 mg / m ² Redox compound: RE-2 20 mg / m ² 2-mercapto-6-hydroxypurine ^{5mg / m 2 EDTA 20mg / m} 2 latex polymer ^{f 0.5g / m 2 S-1} 1.7mg / m 2 formulation 5 (emulsion protective layer composition) solids gelatin 0.6 g / m ² dye AD-5 Body (average particle size ^{0.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² nucleation accelerator: Example Compound Na-3 40mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener: K-1 30 mg / m ² Formulation 6 (Backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² Formulation 7 (hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Interface Activator h 1 mg / m ² Dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener: K-1 20 mg / m ²

[0131]

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[0132]

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[0133]

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(Preparation of silver halide emulsion A) A silver chlorobromide core grain having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which is composed of 70 mol% of silver chloride and the rest is silver bromide, is prepared by using a simultaneous mixing method. Prepared. When the core particles were mixed, K ₃ RuCl ₆ was added in an amount of 8 × 10 ^-8 mol per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ I
3 × 10 ⁻⁷ mol of rCl ₆ was added per mol of silver. The obtained emulsion has an average thickness of 0.10 μm and an average diameter of 0.25.
μm core / shell monodisperse (variation coefficient 10%) (1
Chloroiodobromide (silver chloride 90
Mol%, silver iodobromide 0.2 mol% and the rest silver bromide). Then, JP-A-2-280
Modified gelatin described in JP-A-139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, Japanese Patent Laid-Open No. 2-53967).
-280139, Exemplified compound G-8 on page 287 (3))
It was desalted using. EAg after desalting is 190 mv at 50 ° C
Met.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
After adding 2 × 10 ^-5 mol of chloroauric acid, add 3 × of inorganic sulfur
Chemical ripening was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained by adding 10 ⁻⁶ mol. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole and 3 × 10 ^-4 mol per mol of silver and gelatin. Was added.

(Preparation of Silver Halide Emulsion B) A silver halide emulsion of 60 mol%, silver iodide 2.5 mol%, and silver bromide with an average thickness of 0.05 μm and an average diameter of 0.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. %, The rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Next, JP-A-2-28013
No. 9 described in Japanese Unexamined Patent Publication (Kokai) No. 2-2 (the modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl).
Desalting was carried out using the exemplified compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 180 mv at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
After adding 2 × 10 ⁻⁵ mol of chloroauric acid, N, N, N′-
3 × 1 of trimethyl-N′-heptafluoroselenourea
0 ^-5 mol added to up sensitivity out at a temperature 60 ° C. chemically ripened. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole and 3 × 10 ^-4 mol per mol of silver and gelatin. Was added.

[0138]

[Table 1]

From the above results, from Examples 1 to 3, if the heat treatment temperature and the heat treatment time are the same and the heat treatment time is relatively long, the curl degree of the product wound after the emulsion coating does not depend on the thickness. Be understood.

From the comparison between Examples 4 to 7 and Comparative Examples 1 and 2, the heat treatment temperature of the SPS support, which is preferable for the curling degree of the product, is 40 ° C. to 95 ° C. (Tg), preferably 55.
It is understood that the temperature is from 85 ° C to 85 ° C (Tg-10 ° C).

From the comparison between Examples 8 to 11 and Comparative Example 3,
The heat treatment time of the SPS support which is preferable for the curling degree of the product is 0.1 to 1500 hours, preferably 2 to 200 hours.
It is understood that it is time. If it exceeds 1500 hours, the curl-curling degree improving effect of the product is saturated, and it is unfavorable from the viewpoint of industrial productivity to carry out more than this.

From the comparison between Examples 4 to 11 and Comparative Examples 1 to 3, the calorific value of the endothermic peak developed across Tg was
50 to 1000 mcal / g, preferably 100 mca
It is understood that it is 1 / g or more and 1000 mcal / g or less.

From the comparison of the above Examples and Comparative Examples, it is understood that the curl degree of the silver halide photographic light-sensitive material is 80 m ^-1 or less, preferably 60 m ^-1 or less.

[4] Experiment-2 Treatment of Support Film after Subbing Layer Application Next, an example of heat treatment after the subbing layer application (coating) will be described. The biaxially oriented SPS roll film of A-1 was subjected to surface treatment and undercoat layer coating in the order described above to obtain a roll film. This undercoat layer coating roll film is designated as B-1.

Subsequently, the roll film coated with the undercoat layer was heat-treated according to the following contents, and then coated with a silver halide emulsion according to the contents described above to obtain a product roll film.

Examples 12 to 14 and Comparative Example 4 (Table 2) B-1 roll film was dried at 40 ° C, 55 ° C and 70 ° C for 4 hours.
What was heat-processed for 8 hours shall be Examples 12-14. For comparison, Comparative Example 4 was heat-treated at 35 ° C. for 48 hours.

[0147]

[Table 2]

As is clear from Examples 12 to 14, the one heat-treated at the heat-treatment temperature 40 to 70 ° C. for 48 hours had a small curl curl degree and had good workability and film flatness without any problems. In the heat treatment with the undercoat layer applied, the blocking phenomenon that was a concern did not occur,
The emulsion coating could be carried out without any problems.

On the other hand, in Comparative Example 4, the blocking phenomenon did not occur, but as in Comparative Example 1, since the heat treatment temperature was low, no significant improvement was found in the curl curl and the workability was extremely poor. there were.

From the comparison of the above Examples and Comparative Examples, it is understood that the curl degree of the silver halide photographic light-sensitive material is 80 m ^-1 or less, preferably 60 m ^-1 or less.

[5] Experiment-3 Case of Processing into Film After Coating of Silver Halide Emulsion Layer Next, an example of heat treatment after coating of the silver halide emulsion layer will be described.

Subsequently, the roll film of B-1 was coated with a silver halide emulsion layer as described above to obtain a roll film. This emulsion layer coating roll film is designated as C-1.

Examples 15 to 16 and Comparative Example 5 (Table 3) C-1 roll films are heat treated at 40 ° C. and 70 ° C. for 48 hours to give Examples 15 to 16. For comparison, Comparative Example 5 was heat-treated at 35 ° C. for 48 hours.

[0154]

[Table 3]

As is clear from the examples, the heat treatment temperature of 40
The one heat-treated at ˜70 ° C. for 48 hours had a good curl curl, did not cause blocking, and did not deteriorate in photographic performance. On the other hand, in Comparative Example 5, blocking did not occur, but as in Comparative Examples 1 and 5, since the heat treatment temperature was low, the curl curl degree was not significantly improved.

From the comparison of the above Examples and Comparative Examples, it is understood that the curl degree of the silver halide photographic light-sensitive material is preferably 80 m ^-1 or less.

[6] Experiment-4 In the case of SPS laminated support film Next, an example of the SPS laminated support will be described.

The laminated support was manufactured as follows.

(1) Polymerization of SPS In the above-mentioned polymerization of SPS, with respect to the styrene basic skeleton,
The copolymerization monomer and the amount (mol%) shown in Table 4 were added to obtain an SPS-based copolymer.

(2) Preparation of SPS Film The obtained SPS-based copolymer pellets were dried at 150 ° C. for 3 hours in a nitrogen atmosphere, and the SPS-based copolymer was extruded at 320 ° C. in a separate extruder. The polymer is laminated in a laminated state in a laminating die, melt-extruded into a film, and the laminated sheet is rapidly cooled and solidified on a cooling drum at 40 ° C. by an electrostatic application method to prepare an unstretched film. An unstretched film having a thickness composition ratio of each layer of 990 μm as shown in Table 4 was obtained. This unstretched film was stretched 3.1 times in the machine direction at 125 ° C.
The film was stretched 3.2 times in the transverse direction at 0 ° C., heat-set at 250 ° C. for 30 seconds, and wound with a 100 μm-thick biaxially oriented laminated SPS-based copolymer film to obtain a roll film.

Examples 17 to 24 Comparative Examples 6 and 7 (Table 4) The biaxially oriented laminated SPS copolymer roll film was surface-treated, coated with an undercoat layer and coated with a silver halide emulsion according to the contents described above. Then, product roll films of Examples 17 to 24 and Comparative Examples 6 and 7 were obtained in order.

In the case of a two-layer laminated film, the laminated film is composed of the first layer and the second layer, and there is no third layer. In the case of a three-layer laminated film, it is composed of first to third layers, and the third layer constitutes the central layer. Both the two-layer and three-layer laminated films have the property of curling with the second layer inside, as they are.

An emulsion layer was applied to the first layer of the laminated film and a back coat layer was applied to the second layer, and the emulsion layer side, that is, the first layer side was inwardly wound on a core to obtain a silver halide photographic light-sensitive material. When stored, an anti-curl force that tends to curl with the second layer side, that is, with the back coat layer inside, is generated against the curl curl force generated with the emulsion layer inside, and these forces cancel each other out. It is estimated that a flat film can be obtained when released from the core.

[0164]

[Table 4]

From the results of Examples 17 to 24 and Comparative Examples 6 and 7, the curl degree of the silver halide photographic light-sensitive material was 80 m ^-1.
It will be understood that the workability is excellent if it is below 60 m ⁻¹ , preferably below. At this time, the curl degree is 80 m ^-1 or less if the difference in the copolymerization components of the outermost layers of the laminated film is 3 mol% or more, and the curl is 5 mol% or more and 10 mol% or less. It is understood that a degree of 60 m ^-1 or less can be achieved.

If the proportion of the copolymerization component of the SPS support exceeds 15 mol%, the original characteristics of the SPS support will be lost, so the proportion of the copolymerization component is preferably 15 mol% or less.

[0167]

Industrial Applicability According to the present invention, it has excellent thermal, mechanical, physical, chemical, and optical properties, particularly optical properties (light transmittance, haze, etc.) and dimensional stability (moisture absorption). It is possible to provide a silver halide photographic light-sensitive material having a small expansion coefficient), a small curl curl, and excellent workability and handleability, and a support thereof.

Claims (5)

[Claims] 1. A syndiotactic polystyrene-based support having at least one silver halide emulsion layer,
A silver halide photographic light-sensitive material having a curl degree of 80 m ^-1 or less in a silver halide photographic light-sensitive material wound in a roll. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the curl degree is 60 m ⁻¹ or less. 3. The support for a silver halide photographic light-sensitive material according to claim 1 or 2, wherein the heat quantity of an endothermic peak that develops across the glass transition temperature (Tg ° C.) of the support is 50 to 50. A support for a silver halide photographic light-sensitive material, which is 1000 mcal / g. 4. The glass transition temperature (Tg ° C.) of the support.
The amount of heat of the endothermic peak that develops over 100 to 600
The support for a silver halide photographic light-sensitive material according to claim 3, wherein the support is mcal / g. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the support is a support in which two or more different syndiotactic polystyrene layers are laminated.