JPH07270972A - Roll of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a roll of the silver halide photographic sensitive material superior in mechanical strength flatness, electric conductivity, printing performance, and productivity, and small in curling tendency and deterioration of quality after the processing. CONSTITUTION:The roll of the silver halide photographic sensitive material has at least one photosensitive layer on a polyester film support having a thickness of 50-150mum and heat treated at a temperature ranging from 50 deg.C up to just below the glass transition point Tg and the roll of 15-30mm width is wound on a spool.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and in particular, a machine having a width of 15 to 30 mm and wound on a spool, using a polyester film heat-treated below the glass transition temperature as a support. The present invention relates to a roll-shaped silver halide photographic light-sensitive material excellent in dynamic strength, curling after processing and deterioration of quality thereof, flatness, conductivity, printing performance, and productivity.

[0002]

2. Description of the Related Art A photographic camera is desired to be further miniaturized in consideration of convenience and portability, but in pursuit of miniaturization, the storage space of the photographic film incorporated therein is made compact. Is essential. Usually, a roll of film wound on a spool is built in as a photographic film, so in order to make the space compact and to secure a certain number of shots (for example, 36 shots), It is necessary to reduce the thickness of the film itself. In particular, the thickness of triacetyl cellulose (TAC) film, which is the support for photographic film, is
120-125 μm, and the thickness of the photosensitive layer (25-30
The thickness of this support is considered to be the most effective means for reducing the thickness of the entire photographic film, as it is considerably thicker than the thickness of the photographic film. By the way, since the TAC film originally has weak mechanical strength, if it is thinner than the current one, the strength will decrease. If the film thickness of the support is 100 μm or less, the photosensitive material using the TAC film was developed by a cine type developing machine. At that time, the perforations at the both end portions of the film were broken, which was not practical.

On the other hand, polyethylene terephthalate (PET) has been conventionally known as a support and has been used for an X-ray film and a plate-making film. Due to its excellent strength, application to color negative films is also possible. However, although the polyethylene terephthalate support has excellent strength, it has a low glass transition temperature of about 70 ° C, so it can be stored for a long time by winding the film in a high temperature atmosphere at about 60 ° C, which is equivalent to the storage stability in the summer. The winding curl attached when placed is severely curled by the processor before the development processing, it is inferior in handleability, and there is a drawback that the curling curl is hardly removed even after the development processing, and it is inferior in curl curl resolving ability. I couldn't stand it.

On the other hand, in order to improve the curl after processing,
In JP-A-6-35118 and 6-51437, after applying an undercoat layer to a polyester film to impart conductivity,
The glass transition temperature (hereinafter T
There is known a photosensitive material using polyethylene naphthalate in which curling is less likely to occur by heat treatment at a temperature not higher than g (abbreviated as g) (annealing treatment, sometimes abbreviated as AN hereinafter).

However, when the film is wound on a core for thousands of meters or more in continuous mass production, the wound diameter of the wound state reaches about 1 m, but a polyethylene naphthalate film (hereinafter abbreviated as PEN). ) Originally has a small thermal conductivity, so when annealed in this state, the heat distribution greatly differs between the outside of the winding, which is susceptible to direct heat treatment, and the inside of the winding, which is less susceptible to heat treatment. However, the quality of the curl was large, and the curl performance was still insufficient, and it was not practical.

When annealed, the annealed polyester film does not tend to curl when it is supposed to be stored in the summer, but a polyester film immediately after film formation, which is heat set after biaxial stretching, is extremely difficult. Since it is easy for the curl to stick to the core, the curl will stick to the core when annealing is performed in the rolled state, and it may be due to the bad curl before undercoating or before coating the photosensitive layer. It suffered from the contradictory contradiction that coating unevenness was likely to occur in the coating layer and the photosensitive layer, and it could not be put to practical use.

Further, the undercoating layers on the front and back of the polyester film in the state of being wound by the heat of the annealing treatment are stuck or deteriorated, so that the electrical conductivity (surface specific resistance) is poor and it cannot be put to practical use.

Furthermore, when quality control of the curl by annealing is performed, even if the curl is sampled by measuring the polyester film outside the curl, the curl is greatly related to the viscoelasticity of the polymer. It was found that quality control was not possible even for the winding performance of the winding, and it was necessary to anneal unnecessarily for a long time, resulting in low production efficiency and improvement.

On the other hand, since the photosensitive layer contains gelatin as a component, the emulsion layer contracts significantly after development and the concave curl on the emulsion layer side is severe. In these photosensitive materials, the emulsion layer was wound on a spool having a small diameter. At this time, the curl in the longitudinal direction is easily converted to the width direction and the curl in the width direction is severe. When printing a print using this photosensitive material, the surface of the photosensitive material floats and print blur occurs, which is not practical.

[0010]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide excellent mechanical strength, curl after processing and reduction in quality unevenness, excellent flatness, conductive performance, printing performance, and excellent productivity. The object is to provide a rolled silver halide photographic light-sensitive material.

[0011]

The above object of the present invention can be achieved by any of the following constitutions (1) to (7).

(1) In a roll-shaped silver halide photographic light-sensitive material having at least one photosensitive layer on a polyester film support, the polyester film support has a thickness of 50 to 150 μm and a temperature of 50 ° C. A roll-shaped silver halide photographic light-sensitive material characterized by being heat-treated at a temperature lower than the glass transition temperature (Tg) and wound on a spool with a width of 15 to 30 mm. .

(2) After the polyester film support is heat-fixed by biaxially stretching the polyester film support,
The rolled silver halide photographic light-sensitive material as described in (1) above, which is heat-treated at a temperature of 70 ° C. or higher and lower than the glass transition temperature for less than 0.1 hour before coating the photosensitive layer.

(3) The total sum of heat treatments at a temperature of Tg or more and Tg + 50 ° C. or less after the heat setting of the polyester film support and before the coating of the photosensitive layer is less than 0.1 hour, (1) Alternatively, the rolled silver halide photographic light-sensitive material described in (2).

(4) The absolute value of the curl in the longitudinal direction of the polyester film is 40 m before applying the undercoat layer (undercoat layer) and / or the photosensitive layer to the polyester film.
^-1 or less, The roll-shaped silver halide photographic light-sensitive material described in (1) to (3) above.

(5) The roll-shaped silver halide photographic light-sensitive material described in (1) to (4) above, wherein the polyester film support has a glass transition temperature of 90 ° C. or higher.

(6) The above-mentioned (1) to (5), wherein 50 mol% or more of the dicarboxylic acid component of the polyester film is naphthalene dicarboxylic acid and the glycol component is mainly ethylene glycol. Rolled silver halide photographic light-sensitive material.

(7) The rolled silver halide described in (1) to (6) above, wherein the polyester film has a thermal conductivity of 4.0 × 10 ⁻⁴ cal / cm.sec. ° C. or more. Photographic material.

<Evaluation Method> A method for measuring physical property values of the present invention will be described.

<Glass transition temperature> 10 mg was sampled from the film, set in a scanning scanning calorimeter, and kept at 20 ° C. under a nitrogen stream.
The glass transition temperature was defined as the average value of the temperature at which the baseline started to become biased and the temperature at which the baseline returned to a new baseline, which was raised at a rate of / min.

Lamination, blending of polyester and copolyester, or lamination. Since two or more glass transition temperatures may be observed, the value on the high temperature side was taken as the glass transition temperature in this case.

<< Thermal Conductivity >> The polyester film was measured after humidity conditioning for 2 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 55% RH. It was measured at a temperature of 60 ° C. using a rapid thermal conductivity meter QTM-D3 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

The physical properties of the polyester film are the same as those of the silver halide emulsion layer and / or the gelatin back layer, the undercoat layer, the magnetic recording layer, which are coated on the support of the photosensitive material after the preparation of the photosensitive material. Etc., the same value can be obtained by cutting out the support peeled off using pancreatin, or an aqueous solution of sodium hypochlorite in the same manner, so that substantially the same value can be obtained. May be.

<< Longitudinal curl >> 40 in the longitudinal direction (flow direction of the process) from the sample before undercoating or before coating the photosensitive layer
mm and 2 mm in the width direction, and after controlling the humidity for 1 day in an atmosphere of 23 ° C. and 55%, measure the longitudinal curl using a curl gauge.

The present invention will be described in detail below.

The present invention provides a rolled silver halide photographic light-sensitive material having at least one photosensitive layer on a polyester film support, wherein the polyester film support has a thickness of 50 to 150 μm, and 70 A roll-shaped silver halide photographic light-sensitive material which is heat-treated at a temperature of not less than ° C and lower than the glass transition temperature (Tg) and which is wound on a spool with a width of 15 to 30 mm.

As a method for preventing the print blur of the polyester film, a method in which the amounts of the plasticizers on the front and back sides of the base are made different, as in the TAC support, and anti-curl is applied in advance in the opposite direction to the contraction direction of the emulsion layer. However, even if this method is applied to a polyester base, it is difficult to distribute the plasticizers on the front and back sides in the production by melt extrusion biaxial stretching. Therefore, a method for preventing the curling due to the viscoelasticity of a polymer, a method described in JP-A-51-16358, that is, a method for heat treatment at a glass transition temperature of 5 ° C. or less is used in the present invention. With a film thickness of 50 to 150 μm
And when I applied it when it was wound with a width of 15 to 30 mm, surprisingly, the width was 35 mm and the film thickness was less than 50 μm,
We have also found that print blurring and curling can be prevented more unexpectedly than when it exceeds 150 μm.

This print blur can be prevented by reducing the width and increasing the film thickness. However, the film thickness must be 150 μm or less in order to efficiently obtain the effect of the heat treatment, that is, the effect of suppressing the conversion of the vertical curl into the curl in the width direction, and sufficient performance as a photographic image is obtained. In order for the width to be greater than 15 mm.

From the viewpoint of miniaturization of the camera of the present invention, it is preferable that the spool has a diameter of 10 mm or less. However, in order to suppress the conversion of the vertical curl into the width curl and to obtain the effect of print blur, the spool diameter is preferably 5 mm. ~ 9 mm.

It is preferable to heat-treat this effect at a temperature as high as possible, but this effect disappears at the glass transition temperature (Tg) or higher. This effect becomes significant from above 50 ° C for 2 minutes.

The annealing treatment (AN treatment) of the film is not particularly limited, but the method described in JP-A-51-16358 can be employed, and the heat treatment temperature is preferably 50 ° C. to Tg-10 because of its flatness. ℃, particularly preferably 70 ℃ ~ Tg-10
The treatment time is 1000 ° C. or less when the AN treatment effect and the productivity are combined.

Although the effect increases as the treatment time increases, it is preferable to perform the treatment in a short time in order to improve the productivity. Further, the wound core is subjected to a heat treatment (AN treatment) below the glass transition temperature. In order to prevent winding curl and suppress coating unevenness of the undercoat layer that imparts a function such as conductivity, prevent thermal deterioration of surface specific performance, and reduce quality unevenness outside and inside the roll. After the polyester film support is heat-fixed by biaxially stretching the polyester film support and before coating the photosensitive layer, it is preferable to heat-treat a thin leaf at a temperature of 70 ° C. or more and less than the glass transition temperature for less than 0.1 hour.

The term "thin leaf" as used herein means a sheet-like material which continuously passes through the heat treatment zone. The polyester film support to be heat-treated is in a state where the curl of the film in the machine direction is 40 m ^-1 or less in absolute value. Within this range, for example, it may be conveyed obliquely, vertically or horizontally with respect to the flow direction of film formation, and it is preferable to pass through a heat treatment part in which a plurality of dancer rolls are combined so that it can be accumulated. . By doing so, the undercoating and coating unevenness of the emulsion layer are further reduced, which is preferable. Other than this, the heat treatment may be carried out at a temperature lower than the glass transition temperature and further wound, unless the effect of the present invention is impaired.

This AN treatment may be carried out before or after the biaxial stretching of polyester in the film forming step and the usual cooling treatment performed after heat setting, or may be carried out in the step of applying the undercoat layer. Also, it may be carried out in the step of coating the photosensitive layer, but it is particularly preferable to carry out the film forming step because of the ease of forming the polyester film, and to prevent the deterioration of the surface specific performance, the undercoating before winding into a roll. It is preferably performed in the step after coating the undercoat layer. Furthermore, it is preferable that the heat treatment is performed at this time in a flat and curl-free state. As a method for performing heat treatment, blowing a known hot air, an infrared heater,
A known method such as a far infrared heater can be used, and the heat transfer coefficient is preferably 50 kcal / m ² .h. ° C. or more.

In order to eliminate the uneven coating of the undercoat layer and the uneven coating of the photosensitive layer, the polyester film is coated with an undercoat layer (undercoat layer) and / or a photosensitive layer in the longitudinal direction of the polyester film. The curl is preferably 40 m ^-1 or less, and particularly preferably 20 m ^-1 .

Curl is the reciprocal of the radius of curvature.

Further, in order to eliminate surface specific performance, curling after treatment, and unevenness in quality, heat treatment at a temperature of Tg or more and Tg + 50 ° C. or less after heat setting of the polyester film support and before coating the photosensitive layer. The total time is preferably less than 0.1 hours. Particularly preferably, when the support is annealed, if heat of Tg or higher is applied in the subsequent steps, the curling after the treatment may be deteriorated. It is preferably less than Tg, and it is better not to apply heat above Tg.

Therefore, when the thin film and / or the wound annealing treatment is performed before the subbing step, drying in the subsequent step, that is, the subbing layer, the conductive layer, the magnetic recording layer and other various functional layer coating steps, The heat treatment time is preferably less than 0.1 hours. Further, it is preferably 150 ° C. or less and less than 0.1 hour.

It is preferable that the above heat treatment is long in order to sufficiently dry and harden the undercoat layer when the undercoat layer is applied, but if it is too long, it tends to be curled and the undercoat layer is formed. The heat deterioration of may occur.

Therefore, it is desirable that the subsequent step, that is, the undercoat layer, the conductive layer, the magnetic recording layer, and other various functional layer coating steps be a system in which the film-hardening reaction occurs without applying a heat of Tg or more.

Examples of such a system include a binder used in a constituent layer such as an undercoat layer or a magnetic layer, that is, gelatin,
Hydrophilic binders such as polyvinyl alcohol and acrylic acid type copolymers, or vinyl type polymers and copolymers, cellulose derivatives, polyester resins, acrylic resins, polyurethane resins and other hydrophobic polymers hardened at relatively low temperatures of Tg or lower. A system using a hardening agent that reacts with.

Examples of hardeners that can be used include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), and 2-hydroxy-4,6. -Dichloro-1,3,5-triazine, US Pat. No. 3,288,
775, 2,732,303, British Patent 974,723, 1,16
Reactive halogen-containing compounds described in 7,207, etc., divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, US Pat. Nos. 3,635,718, 3,232,763 , Compounds with reactive olefins described in British Patent No. 994,869, N-hydroxymethylphthalimide, US Pat. No. 2,73
N-methylol compounds described in 2,316, 2,586,168, etc., isocyanates described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280, 2,9
83,611 etc., aziridine compounds, U.S. Pat.Nos. 2,725,294, 2,725,295, etc. acid derivatives, U.S. Pat. No. 3,091,537, etc., epoxy compounds, such as mucochloric acid. And halogen carboxaldehydes. Further, an inorganic hardener can be used, and examples of the inorganic hardener include chrome alum and zirconium sulfate, and Japanese Patent Publication Nos. 56-12853 and 58-32699, Belgium. Japanese Patent No. 825,726, Japanese Patent Laid-Open No. 60-225148, Japanese Patent Laid-Open No. 51-126
125, Japanese Patent Publication No. 58-50699, Japanese Unexamined Patent Publication No. 52-54427, U.S. Pat. No. 3,321,313 and the like can also be mentioned a carboxyl group activated type hardener.

A system that does not require heat for the dura mater reaction is also effective. As such means, active energy rays, that is, ultraviolet rays, visible rays, electron rays, X-rays, α
Examples of the binder system include a binder system that is cured by rays, β rays, and γ rays. At this time, it is preferable to select a hardening reaction system having an absorption characteristic different from that of the polyester film support and using it as an active energy.

Examples of the polymer curable by active energy rays include maleic anhydride type, urethane acryl type, ether acryl type and epoxy acryl type.

The glass transition temperature of the polyester film support is preferably 90 ° C. or higher, and particularly preferably 110 ° C. or higher and 200 ° C. or lower, in order to make it hard to curl and reduce the print blur of the present invention. If the glass transition temperature is too low, curling due to shrinkage of the photosensitive layer may occur, which may cause print blur, and thermal deterioration of the undercoat layer may occur.

In order to reduce the curl and efficiently obtain the effect of the AN treatment, preferably 50 mol% or more of the dicarboxylic acid component of the polyester film is naphthalene dicarboxylic acid, and the glycol component is mainly ethylene glycol. It is preferable that 70 mol% or more of the dicarboxylic acid component is naphthalene dicarboxylic acid from the strength, and the glycol component is 60 mol% or more of ethylene glycol, and more preferably 85 mol% of the dicarboxylic acid component. The above is naphthalenedicarboxylic acid, and the glycol component of ethylene glycol is 90 mol% or more.

From the standpoint of improving the efficiency of the AN treatment and improving the productivity, the thermal conductivity of the polyester film is preferably 4.0 × 10 ⁻⁴ cal / cm.sec. ° C. or higher, particularly preferably 4.5 × 1.
0 ^-4 cal / cm.sec. ° C or higher. In order to increase the thermal conductivity, the intrinsic viscosity of the polyester is reduced, the molecular weight distribution (weight average molecular weight / number average molecular weight) is narrowed, butanediol or the like is appropriately blended as a glycol component, or
It is preferable to adjust by increasing the density and increasing the thermal conductivity.

The intrinsic viscosity of the polyester film is 0.5
(Dl / g) or less is preferable, and it is particularly preferably 0.4 to 0.48 considering the stretchability during film formation.

As the intrinsic viscosity is smaller, the orientation of the crystal part is not broken and the entanglement of the molecular chain of the amorphous part is increased, the thermal conductivity is increased, and the effect of the annealing treatment can be further increased. The intrinsic viscosity can be obtained by controlling the melt viscosity (torque) during the polymerization of the polyester film.

The density of the polyester film is preferably 1.36 (g / cm ³ ) or more, particularly preferably 1.37 to
It is 1.39 (g / cm ³ ). The density can be adjusted by the heat setting temperature during the production of the polyester film, the processing time, and the stretching ratio.

Further, in order to increase the effect of the annealing treatment, the water content of the polyester film before the annealing treatment is increased to the extent that the flatness is not impaired. It is preferable to perform the annealing treatment at a temperature higher than the crystal point temperature and higher than the glass transition temperature.

It is preferable that 1 to 20 mol% of the glycol component of the polyester film is 1,4 butanediol as a copolymerization component, and in consideration of strength, it is preferably 3 to
15 mol% is preferable, and 5 to 7 mol% is particularly preferable.

The polyester film used in the light-sensitive material of the present invention has a surface roughness of 0.003 μm or more from the viewpoint of the effect of AN treatment in a rolled state and the prevention of quality unevenness in winding. The haze is preferably 1.5% or less, particularly preferably the surface roughness is 0.005 μm or more and the haze is 1% or less. The larger the surface roughness, the more easily the heat conduction from the hot air in the annealing process in the rolled state is likely to occur efficiently, which helps prevent unevenness in quality.In terms of photographic performance, the surface roughness is particularly preferably 0.005 μm to 0.01 μm
And the haze is 1% or less.

Examples of the naphthalenedicarboxylic acid used in the present invention include 1,2-naphthalenedicarboxylic acid and 1,3-
Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid Acid, 2,4-
Examples thereof include naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 2,8-naphthalenedicarboxylic acid. Of these, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable. Glycol has ethylene glycol as a main component, but other components may be copolymerized or // unless the effects of the present invention are impaired.
And other polyesters may be blended.

For example, as the other dicarboxylic acid component,
Aromatic dibasic acid is preferable, and as the main constituent dicarboxylic acid component, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, cyclohexane dicarboxylic acid, There are diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, phenylindane dicarboxylic acid, etc., and other glycol components include propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, p- Xylylene glycol,
2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4
-Hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether and the like, and 1,4-butanediol is particularly preferable as the copolymerization component.

Furthermore, unless the effects of the present invention are impaired,
An aromatic dicarboxylic acid having a metal sulfonate group may be added as a copolymerization component of the dicarboxylic acid component in the polyester to further improve the curling after the treatment. For example, 4-sodium sulfo-2,6-naphthalene. Dicarboxylic acid, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoisophthalic acid,
And their ester-forming derivatives, and these sodium with other metals (potassium, lithium, etc.)
In addition, a compound substituted with, or a polyalkylene glycol and / or a derivative thereof in order to increase the thermal conductivity may be contained.

Examples of the polyalkylene glycols and / or derivatives thereof include compounds having a repeating structure of an alkyleneoxy group, such as polyalkylene glycol and polyalkyleneoxydicarboxylic acid, and the number average molecular weight is preferably 300 to 10,000, Particularly preferably 10
It is from 00 to 5000.

The copolymerized polyester used in the present invention may be further copolymerized with other components, or may be blended with other polymers, as long as the effects of the present invention are not impaired. The intrinsic viscosity of the preferred polyester is preferably 0.5 or less, particularly preferably 0.4 to 0.
48.

The film of the present invention may be composed of a single layer of polyester, and when laminated, any number of layers such as two layers and three layers may be laminated. Generally, two layers or three layers are preferable from the viewpoint of complication. The polyester layer of the present invention has a thickness of 2 μm or more, and the undercoat layer and the like are not included therein.

[Single-Layer Polyester Film] In the present invention, in order to counter the contraction force of the emulsion layer from the handling property before coating after coating the photosensitive layer, when the polyester layer is composed of a single layer, for example, a film of In the film formation, it is more preferable to provide a temperature difference between the front and back of the film during longitudinal stretching to perform longitudinal stretching, or to provide a temperature difference between the front and back for heat setting during heat setting.

Further, it is possible to improve the handleability before the treatment by infiltrating an organic solvent or the like into one surface of the single-layer film and subjecting it to a heat treatment for solvent treatment.

[Structure of Laminated Polyester Film] When the film of the present invention is laminated, the thickness of each layer can be appropriately determined depending on the polyester and the copolyester used, but when various polyesters having different thermal conductivities are used. When there are three or more layers, it is preferable to laminate a polyester or copolymerized polyester layer having a high thermal conductivity on the outer layer and a polyester layer having a lower thermal conductivity on the inner layer.

When various polyesters having different water absorption properties are used, unless the effect of the present invention is impaired, in the case of three or more layers, the outer layer is made of a polyester or a copolyester layer having a high water absorption rate because of the winding after the treatment. It is preferable to laminate a polyester layer having a smaller water absorption rate than the inner layer.

When the film of the present invention is laminated, the layer structure, film thickness, amount of copolymerization components and the like are appropriately adjusted, and the layer structure is asymmetrical above and below the plane where the polyester film of the present invention is divided into two parts. It is preferable to improve the handleability before the treatment.

The asymmetry referred to here is not particularly limited, but, for example, the order of constitution of the polyester layer or the copolyester layer above and below, the thickness of the layer, and the amount of the main constituent component of the polyester species above and below the half-divided surface are as follows. It is also included that they are different or that the copolymerization component or the amount of the copolymerization component is different.

Further, the film forming method, the solvent treatment and the like as described for the single layer film may be further used for the laminated support.

However, in the case of laminating, considering the cuttability, the adhesiveness between the polyester layer and the copolyester layer is required, and the adjoining polyester layer and / or the copolyester layer are similar in composition, Since it is preferable that the polyester layer and the copolyester layer are blended, the adhesiveness may be inferior and the effect of preventing the print blur of the present invention cannot be sufficiently obtained by this alone.

Both the polyester and the copolyester used in the present invention are phosphoric acid, phosphorous acid and their esters and inorganic particles (silica, kaolin, calcium carbonate,
Calcium phosphate, titanium dioxide, etc.) may be contained, or the polymer may be blended with inorganic particles after polymerization. Further, a pigment, an ultraviolet absorber, an antioxidant, etc. may be added appropriately at any stage of the polymerization and after the polymerization. Examples of preferable antioxidants include hindered phenol-based ones.

To obtain the polyester resin constituting the support of the present invention, melt polymerization may be carried out after the above-mentioned copolymerization component is added after transesterification, or the copolymerization component may be added before transesterification and melted. Polymerization may be carried out, or may be carried out using a known transesterification catalyst or synthetic method such as solid phase polymerization of a polymer obtained by melt polymerization.

It is also possible to obtain the product by directly transposing it through a diglycol ester of glycol and dicarboxylic acid without transesterification with dicarboxylic acid. Further, the process conditions such as the temperature during the polymerization can be appropriately adjusted as long as the effects of the present invention are not impaired. The polyester film used in the present invention may contain various additives. For example, in order to prevent the light piping phenomenon (flickering) that occurs when light enters the film coated with a photographic emulsion layer from the edge,
A dye may be added to the polyester film. The type of film dye is not particularly limited, but those having excellent heat resistance are preferable in the polyester film forming process, and examples thereof include anthraquinone chemical dyes. Further, as a film color tone, gray dyeing is preferable as seen in general light-sensitive materials, and one kind or two or more kinds of dyes may be mixed and used.

Since the polyester film using naphthalene dicarboxylic acid easily absorbs light having a short wavelength and emits fluorescence, it is preferable to further contain an ultraviolet absorber or a known fluorescence quencher in the polyester.

A method for producing a polyester film having a single layer according to the present invention will be described.

The unstretched sheet may be obtained by a conventionally known method. For example, after sufficiently drying the obtained resin, it is melt-extruded into a sheet through a filter and a die and cast on a rotating cooling drum to be cooled and solidified. There is a method.

As a method of biaxially stretching the finished sheet, the following processes (A) to (D) can be adopted in the biaxial direction in the temperature range of glass transition temperature (Tg) to Tg + 100 ° C.

(A) A method in which an unstretched sheet is first stretched in the machine direction and then is stretched in the transverse direction. (B) A method in which an unstretched sheet is first stretched in the transverse direction and then in the machine direction (C) Unstretched. A method in which a sheet is stretched in the longitudinal direction in one or multiple stages, then stretched in the longitudinal direction again, and then stretched in the lateral direction (D) An unstretched sheet is stretched in the longitudinal direction in one or more stages and then in the transverse direction. A method of stretching and then stretching in the longitudinal direction again.

The above stretching is preferably in the range of 4 to 20 times in terms of area ratio in order to obtain the required elastic modulus of the polyester film. The heat setting can be performed in the temperature range of 150 to 240 ° C. Preferably, the modulus of elasticity in the length and width is 60 rather than strength
It is preferably 0 kg / mm ² or more.

The method for producing the laminated film of the present invention includes, for example, melt-extruding polyester and copolyester from separate extruders, and then forming a laminar flow in the conduit of the melted polymer or the extrusion die. A method of extruding by joining in multiple layers, cooling and solidifying on a cooling drum to obtain an unstretched film, then biaxially stretching and heat setting, or melt extruding a polyester or copolymerized polyester simple substance and a laminated film from an extruder and cooling. The unstretched film cooled or solidified on the drum or the surface of the uniaxially oriented film uniaxially stretched the unstretched film, if necessary, an anchor agent, a polyester or a copolymerized polyester simple substance on it after coating an adhesive, etc., Extrusion laminate the laminated film, then heat set after completing biaxial stretching And the like custo Lou John lamination methods, co-extrusion method from simplicity of process is preferred.

In this case, the stretching conditions of the film are not particularly limited, but generally, in the temperature range of Tg from the glass transition temperature (Tg) of the polyester layer or the copolymerized polyester layer, which is higher, to Tg + 100 ° C., the film is biaxially oriented. The methods A to D can be adopted in the same manner as the stretching method for the single-layer polyester layer. The stretching ratio is preferably in the range of 4 to 20 times in terms of area ratio. The heat setting can be performed in the temperature range of 150 to 240 ° C. Preferably, the vertical and horizontal elastic modulus is 600 kg
/ Mm ² or more is preferable.

The film of the present invention has at least one silver halide emulsion layer on at least one side thereof or on the convex side of the support under an atmosphere of 23 ° C. and 55% RH. A rolled silver halide photographic light-sensitive material is constituted. This silver halide emulsion layer can be directly coated on the support or can be coated through another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the silver emulsion layer. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, you may provide the intermediate layer which consists of hydrophilic colloids as needed. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer or a backing layer may be provided between the silver halide emulsion layer and the protective layer. Further, a magnetic recording layer or the like may be provided on the side opposite to the silver halide emulsion layer.

As a method for providing the magnetic recording layer on the support, a known method can be used, preferably by multi-stripe coating.

The thickness of the magnetic recording layer is preferably 0.1 to 10 μm, more preferably 0.5 to 3 μm. The coating liquid for forming the magnetic recording layer contains a lubricant, an antistatic agent, etc. in order to impart functions to the magnetic recording layer such as imparting lubricity, antistatic property, antiadhesive property, friction, and rubbing property. Various additives can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and a clogging of the magnetic head are prevented. An abrasive can be added for this purpose.

In the present invention, it is preferable to add an antistatic agent also in order to prevent generation of fogging due to static electricity, and examples thereof include metal oxide particles.

The polyester film of the present invention has improved adhesiveness and improved wetting characteristics of the coating liquid.
If necessary, various surface treatments such as corona discharge treatment, chemical treatment, flame treatment and the like can be performed in advance. Of these, corona discharge treatment is most preferably used. The polyester support of the present invention preferably has an undercoat layer in order to increase the adhesive force with a photographic layer such as a photosensitive layer coated thereon. Examples of the subbing layer include a subbing layer using a polymer latex made of a styrene-butadiene copolymer or a vinylidene chloride copolymer, and a subbing layer using a hydrophilic binder such as gelatin. The undercoat layer preferably used in the present invention is a subbing layer using a hydrophilic binder. Examples of the hydrophilic binder used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers and maleic anhydride copolymers, and of these, gelatin is particularly preferable. Examples of the compound that swells the polyester film used in the present invention include resorcin and / or a derivative thereof, a cresol compound, a chloro-substituted product of phenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and the like. Among these, resorcin and p-chlorophenol are preferable.

Various gelatin hardeners can be used in the undercoat layer of the present invention. Examples of gelatin hardening agents include chromium salts, aldehydes, isocyanates, and active halogen compounds. The undercoat layer of the present invention may contain inorganic fine particles such as silicon dioxide or titanium dioxide, or polymethylmethacrylate copolymer fine particles as a matting agent.

Since the polyester film using naphthalenedicarboxylic acid easily absorbs light having a short wavelength and emits fluorescence, it is preferable to further contain an ultraviolet absorber or a known fluorescence quencher in the undercoat layer.

The undercoat layer according to the present invention can be coated by a known coating method.

The silver halide used in the silver halide roll-shaped silver halide photographic material of the present invention may have any composition. Examples are silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide and silver iodobromide. The silver halide emulsion used in the present invention includes a sensitizing dye, a plasticizer,
Antistatic agents, surfactants, hardeners and the like can also be added.

To develop the silver halide roll silver halide photographic light-sensitive material of the present invention, for example, the method described in T. H.
James The Theory of the Photographic Process 4th Edition
Process, Fourth Edition) pages 291-334 and Journal of the American Chemical Society, 73rd.
Vol. 3, page 3100 (1951), a developer can be used.

[0089]

The present invention will be described in more detail with reference to the following examples.

Example 1 and Comparative Example 1 <Production of Polyester> 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 56 parts by weight of ethylene glycol, 1,4-
4.1 parts by weight (5 mol%) of butanediol was added, 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out by a conventional method. Then, 0.04 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate were added to the obtained product. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 285 ° C. and 0.5 mmHg to obtain a polyester (M) having an intrinsic viscosity of 0.5. The respective glass transition temperatures were as shown in Table 2.

<Preparation of Support> The obtained polyester was vacuum-dried at 150 ° C., melt-extruded from a T-die at 300 ° C. using an extruder, and rapidly cooled and solidified in a cooling drum to give an unstretched film. Obtained. Then, when each glass transition temperature (Tg) was set, longitudinal stretching (3.2
23 times), and then transversely stretch at a temperature of 125 ° C (3.4 times), and
Heat set at 0 ° C, then cool with warm air at 30 ° C for 1 minute, and then wind around a winding core (diameter 30 cm) with a diameter of 1 m.
A biaxially stretched film having a thickness of 90 μm was obtained. (Less than,
It may be called a support.) <Preparation of photosensitive material><Tin oxide dispersion liquid> Ishihara Sangyo Co., Ltd. Antimony-doped tin oxide SN-100P powder 400 g and a mixed solution of water 600 g pH 7.
After adjusting to 0, dispersion was performed with a stirrer and a sand mill to prepare a dispersion liquid A.

<Preparation of Photosensitive Material> The prepared support was subjected to undercoating as described below to form a back layer and an emulsion layer.

Both sides of the support were subjected to a corona discharge treatment of 8 W / (m ² · min). On one side of the support, the undercoat coating liquid A
-1 is applied to a dry film thickness of 0.8 μm to form an undercoat layer A-
1 is formed on the undercoat layer A-1 and 8 W / (m ² · mi
n) is subjected to corona discharge, and the following subbing coating solution A-2 is applied onto the subbing layer A-1 to give a dry film thickness of 0.1 μm.
Formed 2.

On the other surface of the support, the following coating solution B-1 was applied.
To a dry film thickness of 0.6 μm to form a conductive layer B-
1 was formed.

<Undercoating liquid A-1> Copolymerized latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyacrylate (solid content: 30% ) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating liquid A-2> Gelatin 10g Compound (UL-1) 0.2g Compound (UL -2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle diameter 3 μm) 0.1 g Finish with water 1000 ml In the following formulation, LX-1 represents a latex.

<Coating Liquid B-1> Aqueous dispersion of LX-1 (solid content 30% by weight) 270 g Compound (UL-1) 0.6 g Dispersion A 560 g Finish with water
1000 ml <LX-1> 5-sulfoisophthalic acid 5 mol% isophthalic acid 15 mol% terephthalic acid 30 mol% ethylene glycol 25 mol% diethylene glycol 25 mol% (average particle size 60 nm)

[0097]

[Chemical 1]

Furthermore, on the conductive B-1, 8 W / (m ² · mi
Corona discharge (n) was applied, and the following coating liquid MC-1 was applied to a dry film thickness of 1 μm.

<MC-1> Nitrocellulose 35% by weight Polyurethane resin 35% by weight Lauric acid 1% by weight Oleic acid 1% by weight Butyl stearate 1% by weight Cyclohexanone 75% by weight Methyl ethyl ketone 150% by weight Toluene 150% by weight Co deposition γ -Fe ₂ O ₃ (long axis 0.2 μm, short axis 0.02 μm, Hc = 650 Oe) 5% by weight Further, the following coating solution OC-2 was applied on the MC-1 coating layer.
It was applied so as to be ml / m ² .

<OC-2> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml After heat fixing, the mixture was stored at 23 ° C. for 3 days, and then subbing was applied. The coating of the undercoat layer and the back layer was performed at a line conveying speed of 50 m, and after coating, hot air was blown to dry at 100 ° C. for 30 seconds (0.5 minutes), and for hardening, heat treatment was performed at 140 ° C. for 2 minutes.

After that, annealing treatment was performed by blowing hot air (heat transfer coefficient 100 kcal / m ² .h. ° C. from both sides) at the temperature shown in Table 2 for 3 minutes, and then the winding core (diameter 30 cm) had a diameter of 1 m. I wound it up.

After coating the undercoat layer at 23 ° C. for one day after coating, an emulsion layer was coated on the side opposite to the back layer of the polyester film in the following manner to prepare a wide photosensitive material.
(Sample Nos. 1 to 5) <Coating of emulsion layer> 25 W / on the undercoat layer A-2.
Corona discharge of (m ² · min) was applied, and the following photographic constituent layers were sequentially formed to prepare a multilayer color photographic light-sensitive material.

The coating amount in the photographic constituent layers shown below is the amount expressed in g / m ² unit in terms of metallic silver for silver halide and colloidal silver, and for couplers and additives. The amount in g / m ² is shown, and for sensitizing dyes, it is shown as the number of moles per mole of silver halide in the same layer.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD- 2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (Di-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C-1) ) 0.33 Colored Nkapura (CC-1) 0.013 DIR compound (Di-1) 0.02 High boiling solvent (OIL-1) 0.16 Gelatin 0.79 Fifth Layer: High Sensitivity Red-Sensitive Layer.

Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ⁻⁵ Cyan Coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium sensitivity green-sensitive layer silver iodobromide emulsion B 0.30 silver iodobromide emulsion C 0.34 sensitizing dye (SD-6) 1.2 × 10 -4 sensitizing dye (SD-7) 1.2 × 10 -4 sensitizing dye SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (Di-2) 0.025 DIR compound (Di-3) 0.002 High boiling solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: High sensitivity green sensitive layer.

Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 ⁻⁵ Sensitizing dye (SD-7) 7.1 × 10 ⁻⁵ Sensitizing dye (SD-8) 7.1 × 10 ⁻⁵ Magenta Coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL) -2) 0.19 gelatin 1.10 12th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 increase Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (Di-4) 0.04 DIR compound (Di-5) 0.02 High boiling solvent (OIL- 2) 0.42 Gelatin 1.40 13th layer: High-sensitivity blue-sensitive layer.

Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1 and dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0109]

[Table 1]

The samples were simultaneously coated with a multi-slide hopper type coater, the first layer to the eighth layer at the first time, and the ninth layer to the fifteenth layer on the second time at the same time.
The coated light-sensitive material was cooled and dried at 18 ° C. for 30 seconds, 5 ° C. for 30 seconds, and then dried at 20 ° C. and 40% relative humidity for 1 minute.
Then, it was wound into a roll, and the humidity was adjusted at 40 ° C. and 50% RH for 2 days to obtain a wide photosensitive material. The sample silver coating amount is 6.25g
/ M ² , dry film thickness is 18 μm, and specific photographic sensitivity is ISO 420
Met.

[0111]

[Chemical 2]

[0112]

[Chemical 3]

[0113]

[Chemical 4]

[0114]

[Chemical 5]

[0115]

[Chemical 6]

[0116]

[Chemical 7]

[0117]

[Chemical 8]

[0118]

[Chemical 9]

[0119]

[Chemical 10]

[0120]

[Chemical 11]

That is, a thin leaf has a total of 3.5 minutes for annealing at 50 ° C. or higher and lower than the glass transition temperature, and 2 minutes for heat treatment at the glass transition temperature or higher.

Thereafter, the width was cut into 10 to 35 mm using a slitter as shown in Table 2, and the evaluation results are shown in Table 2. (Sample Nos. 1 to 5) <Evaluation Method> A method for measuring physical property values of the present invention will be described.

<Glass transition temperature> 10 mg was taken from a polyester film, set in an inspection scanning calorimeter, and heated at a rate of 20 ° C./min under a nitrogen stream, and the temperature at which the baseline began to become eccentric. And the temperature at which the temperature returns to a new baseline are defined as the glass transition temperature.

Lamination, blending of polyester and copolyester, or lamination. Since two or more glass transition temperatures may be observed, the value on the high temperature side was taken as the glass transition temperature in this case.

<< Thermal Conductivity >> The polyester film was measured after humidity conditioning for 2 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 55% RH. It was measured at a temperature of 60 ° C. using a rapid thermal conductivity meter QTM-D3 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

These physical properties of the polyester film are the same as those of the silver halide emulsion layer and / or the gelatin back layer, the subbing layer, the magnetic recording layer coated on the support of the photosensitive material after the preparation of the photosensitive material. Etc., the same value can be obtained by cutting out the support peeled off using pancreatin, or an aqueous solution of sodium hypochlorite in the same manner, so that substantially the same value can be obtained. May be.

<< Longitudinal curl >> 40 in the longitudinal direction (flow direction of the process) from the sample before undercoating or before coating the photosensitive layer.
mm and 2 mm in the width direction, and after controlling the humidity for 1 day in an atmosphere of 23 ° C. and 55%, measure the longitudinal curl using a curl gauge.

The evaluation methods used will be described below.

<< Coating unevenness >> A polyester film after subbing is cut out in a length of 1 m and one full width sample is randomly cut out,
The degree of the interference unevenness was visually evaluated and ranked according to the following criteria.

Note that the practicality in this ranking is
It is determined on the basis of acceptability as a photographic support, and it is considered that there is practically no problem if the rank is Δ or higher.

◯: Good Δ: Interference unevenness can be seen by looking closely ×: Interference unevenness occurs over the entire width or can be seen immediately <Surface specific resistance> Five photosensitive materials in the winding are used and used in the market. It was developed with a short-time developing processor (minilab type). After humidity conditioning for 24 hours in an atmosphere of 23 ° C and 24% RH,
Under the same conditions, a teraform meter VE-30 manufactured by Kawaguchi Denki Co., Ltd. was used to measure the surface resistivity of both surfaces at an applied voltage of 100 V, and the average value was calculated.

The ranking was based on the following criteria. Determined based on acceptability as a photographic support, and rank △
When it is above, there is no problem in practical use, but ◯ or more, and particularly ◎ is preferable.

⊚: 1 × 10 ⁹ Ω / □ or less on both sides ○: 1 × 10 ¹⁰ Ω / □ or less on both sides Δ: 1 × 10 ¹¹ Ω / □ or less on both sides ×: 1 × 10 ¹¹ Ω / at least on one side Beyond □ 《Curling curl and unevenness in quality after treatment》 During annealing, the length is 120 cm taken from the outside and inside of the winding, and the width is 8 mm and 5 samples are used. After that, it was treated at 60 ° C for 6 hours, assuming storage in the summer.
After that, development processing was performed for a short time in the same manner as described above, and the curl was measured and evaluated in the following three stages. The curl of the measured value is the reciprocal of the radius of curvature (unit: m).

Evaluation was carried out on the following three levels from the average of five lines.
There is no problem in terms of performance of photographic film, but it is preferable that
It is the above grade.

◯: 25 m -1 or less Δ: 25 to 45 m -1 x: Exceeds 45 m -1 Further, the quality unevenness was evaluated in four stages from the above evaluation. Although there is no problem with C in the performance of the photographic film, it is preferably B or higher grade.

A: Both inside and outside of the roll B: Either inside or outside of the roll is Δ, and the other is ○ C: Both inside and outside of the roll is Δ D: There is a grade of 《Print blur> Width 35 mm , A 120 cm long light-sensitive material was used, and the images were pre-printed by layering the film on which the landscape was photographed in advance.

After that, development processing was performed, and 100 sheets were printed using a photographic printing machine used in the market.

The test subject was asked to list the number of prints that were blurred by visual evaluation, and the occurrence rate was evaluated according to the following three grades.

Although there is no problem with Δ in terms of the performance of the photographic film, a grade of ◯ or higher is preferable.

◯: Occurrence rate of 2% or less Δ: Occurrence rate of 2 to 5% ×: Exceeded 5% The rolled silver halide photographic light-sensitive material in the present invention was useful for photography. Further, the sample No. 5 having a width of 10 mm was not suitable for photography because the printing operation and evaluation could not be performed, and there were many scratches and the curl of the width was inferior.

Example 2 and Comparative Example 2 Using the polyester obtained in Example 1, an unstretched film was similarly obtained using an extruder. At this time, the drawing speed of the cooling drum was changed to obtain unstretched films having different thicknesses.

Thereafter, in the same manner as in Example 1, biaxial stretching,
Heat setting was performed to obtain a polyester film having a film thickness shown in Table 2.

In the same manner as in Example 1, undercoating, back layer coating and annealing were performed. Then, a photosensitive layer was similarly coated to obtain a photosensitive material shown in Table 2. The evaluation results are shown in Table 2.
(Sample Nos. 6 to 9) Example 3 and Comparative Example 3 In the same manner as in Example 1, a biaxially stretched polyester film having a film thickness of 90 μm was obtained. Thereafter, undercoating, coating of a back layer, and annealing were performed in the same manner as in Example 1 except that the annealing temperature was changed as shown in Table 2. Then, a photosensitive layer was similarly coated to obtain a photosensitive material shown in Table 2. The evaluation results are shown in Table 2. (Sample No. 10 to 14) The film thickness must be 50 to 150 μm, and the annealing treatment below the glass transition temperature must be 50 ° C. or higher. The effect of the present invention cannot be obtained when the annealing treatment is performed at the glass transition temperature or higher. For thin leaves, 70 ° C or higher is preferable.

By the way, in Sample No. 14, the heat treatment at the glass transition temperature or higher takes 5.5 minutes in total.

Example 4 <Production of Polyester> 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 112 parts by weight of ethylene glycol, 79 parts by weight of dimethyl terephthalate (50 mol%) were added, and calcium acetate was used as an ester exchange catalyst. 0.1 part by weight of the hydrate was added and the transesterification reaction was carried out by a conventional method. Then, 0.04 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate were added to the obtained product. Then, the temperature is gradually raised and the pressure is reduced, and polymerization is performed at 285 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.5 (MP1: sample No. 1
6 polyester) was obtained.

Similarly, the terephthalic acid component was adjusted to 70 mol% and 0 mol% of the dicarboxylic acid so that the copolyester (MP2: polyester of sample No. 15) and polyethylene-2,6-naphthalate (PEN: Sample No. 17) was obtained. The glass transition temperature is shown in Table 2.

<Preparation of Support> The obtained copolyester was dried in vacuum at 150 ° C. and then at 295 ° C. using an extruder.
Was melt-extruded from a T-die and rapidly cooled and solidified in a cooling drum shape to obtain an unstretched film. Then, after preheating to Tg + 10 ° C, longitudinal stretching (3.1 times) was performed, and then transverse stretching at Tg + 15 ° C (3.
Heat setting and cooling were carried out in the same manner except that the biaxially stretched film having a thickness of 90 μm shown in Table 2 was obtained.

Thereafter, undercoating, coating of a back layer, and annealing were performed in the same manner as in Example 1 except that the annealing temperature was set as shown in Table 2. Then, a photosensitive layer was similarly coated to obtain a photosensitive material shown in Table 2. The evaluation results are shown in Table 2.
(Sample No. 15-17) Polyester glass transition temperature is 90
A temperature of not less than 0 ° C is particularly preferable.

Example 5 A biaxially stretched polyester film having the same composition and a thickness of 90 μm was obtained in the same manner as in Example 1.

Thereafter, the annealing temperature for thin leaves was 90 ° C. and the time was 1 minute, 5 minutes, and 10 minutes, except that shown in Table 2 (Table 2 is the sum of 0.5 minutes of the treatment at 100 ° C. in the subbing). In the same manner as in Example 1, undercoating, coating of the back layer, and annealing were performed. Then, a photosensitive layer was similarly coated to form
A light-sensitive material shown in was obtained. The evaluation results are shown in Table 2. (Sample Nos. 18 to 20) Example 6 In the same manner as in Example 1, a biaxially stretched polyester film having the same composition and a thickness of 90 μm was obtained. 50 after winding with a diameter of 1 m
Undercoating, coating of a back layer, and annealing were performed in the same manner as in Example 1 except that the humidity was adjusted in an atmosphere of 20 ° C. and 20% RH for 24 hours.
Then, a photosensitive layer was similarly coated to obtain a photosensitive material shown in Table 2. The evaluation results are shown in Table 2. (Sample No. 21) Example 7 A biaxially stretched polyester film having the same composition and a thickness of 90 μm was obtained in the same manner as in Example 1.

Thereafter, undercoating and back layer coating and annealing were carried out in the same manner as in Example 1 except that the annealing temperature was set as shown in Table 2. After winding at a diameter of 1 m, 40 ° C., 50% RH
A light-sensitive material shown in Table 2 was obtained by applying a light-sensitive layer in the same manner except that the humidity was controlled in the above atmosphere for 1 week. The evaluation results are shown in Table 2. (Sample No. 22) In comparison with Sample No. 1, it is preferable that the longitudinal curl before undercoating and coating of the photosensitive layer is 40 m ^-1 or less due to uneven coating and uneven coating of the emulsion layer.

Example 8 Using the same polyester as in Example 1, biaxial stretching and heat setting were carried out, and then hot air (heat transfer coefficient 70 kcal / m ² .h. ° C. from both sides) was blown in the film forming process. After the annealing treatment shown in (1), the film was cooled to obtain a biaxially stretched polyester film having a film thickness of 90 μm.

Thereafter, undercoating and back layer coating were performed in the same manner as in Example 1 except that the annealing was omitted. Then, a photosensitive layer was similarly coated to obtain a photosensitive material shown in Table 2. The evaluation results are shown in Table 2. (Sample No. 23) Example 9 A biaxially stretched polyester film having a thickness of 90 μm was obtained in the same manner as in Example 1.

Thereafter, undercoating and back layer coating and annealing were carried out in the same manner as in Example 1 except that the heat treatment for the undercoating at 140 ° C. for hardening was carried out for 5 minutes and 10 minutes. Then, a photosensitive layer was similarly coated to obtain a photosensitive material shown in Table 3. The evaluation results are shown in Table 3. (Sample Nos. 24 and 25) The heat treatment exceeding the glass transition temperature is preferably less than 0.1 hours.

Example 10 <Preparation of support> The polyester (M) obtained in Example 1 and the polyethylene-2,6-naphthalate (PEN) obtained in Example 4 containing no terephthalic acid component were each added to 150 parts. After vacuum-drying at ℃, melt extrusion at 300 ℃ using 3 extruders, M layer, PEN layer each layer ratio is 3 layers M
A layered unstretched film was obtained by joining the layers in a T-die so as to be composed of a material of / PEN / M = 3/3/1 and rapidly solidifying in a cooling drum. Then longitudinally stretched at 130 ℃ (3.2 times)
Later, after transverse stretching (3.4 times) at a temperature of 135 ° C, heat setting was performed at 240 ° C, followed by cooling with warm air at 30 ° C for 1 minute and winding, and biaxial stretching with a film thickness of 90 μm shown in Table 3. I got a film.

Thereafter, in the same manner as in Example 1, subbing, backing layer and annealing treatment were carried out, an emulsion layer was coated to prepare a light-sensitive material, and evaluation results are shown in Table 3. (Sample No. 2
6)

[0157]

[Table 2]

[0158]

[Table 3]

[0159]

INDUSTRIAL APPLICABILITY According to the present invention, a roll-shaped silver halide photographic light-sensitive material excellent in mechanical strength, curling after treatment and unevenness in its quality, excellent in flatness, conductive performance, printing performance and productivity. Can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 3/00 560 T 3/02 Z

Claims (7)

[Claims] 1. A roll-shaped silver halide photographic light-sensitive material comprising a polyester film support and at least one photosensitive layer, wherein the polyester film support has a thickness of 50 to 150 μm and a temperature of 50 ° C. or higher. A roll-shaped silver halide photographic light-sensitive material, characterized in that it is heat-treated at a temperature lower than the glass transition temperature (Tg) and the roll-shaped silver halide photographic light-sensitive material is wound around a spool with a width of 15 to 30 mm. 2. A heat treatment for a thin film at a temperature of 70 ° C. or higher and lower than the glass transition temperature for less than 0.1 hours after the polyester film support is heat-set by biaxially stretching the polyester film support and before coating the photosensitive layer. The rolled silver halide photographic light-sensitive material according to claim 1, wherein 3. The total heat treatment at a temperature of Tg or more and Tg + 50 ° C. or less after the heat setting of the polyester film support and before the coating of the photosensitive layer is less than 0.1 hours. The rolled silver halide photographic light-sensitive material as described in 1. 4. The absolute value of curl in the longitudinal direction of the polyester film before applying an undercoat layer (undercoat layer) and / or a photosensitive layer to the polyester film is 40 m ⁻¹ or less. The rolled silver halide photographic light-sensitive material according to claim 1. 5. The rolled silver halide photographic light-sensitive material according to claim 1, wherein the polyester film support is a polyester having a glass transition temperature of 90 ° C. or higher. 6. The roll halogenated product according to claim 1, wherein 50 mol% or more of the dicarboxylic acid component of the polyester film is naphthalenedicarboxylic acid and the glycol component is mainly ethylene glycol. Silver photographic light-sensitive material. 7. The thermal conductivity of the polyester film is
7. The rolled silver halide photographic light-sensitive material according to claim 1, which has a temperature of 4.0.times.10.sup.- ⁴ cal / cm.sec..degree. C. or higher.