JP2864077B2 - Silver halide photographic material - Google Patents

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 more particularly, to a method of forming a photographic material at 50.degree.
The present invention relates to a photographic light-sensitive material which is hardly curled, using a polyester which has been heat-treated at a temperature not higher than the glass transition temperature and has a glass transition temperature of not lower than 90 ° C. and not higher than 200 ° C.

[0002]

BACKGROUND OF THE INVENTION Photographic light-sensitive materials are generally prepared by coating at least one photographic light-sensitive layer on a plastic film support. As the plastic film, a fiber-based polymer represented by triacetyl cellulose (hereinafter referred to as (TAC)) and a polyester-based polymer represented by polyethylene terephthalate (hereinafter referred to as (PET)) are generally used. I have.

[0003] In general, photographic light-sensitive materials include sheet-like materials such as X-ray films, plate making films and cut films, and general cameras which are housed in a patrone at a width of 35 m / m or less. And a roll-shaped form typified by a color or black-and-white negative film used for photographing.

As a support for a roll film, TA is mainly used.
C is used, but the greatest feature is that it has no optical anisotropy and high transparency. There is one more excellent feature, which is that it has excellent properties in terms of curl removal after development. That is, the TAC film has a relatively high water absorbency as a plastic film as a characteristic derived from its molecular structure. The molecular chains that flow and become immobilized over time cause rearrangement.

As a result, it has an excellent property that the curl once formed is eliminated. TAC like this
In a photographic photosensitive material using a film having no curl recovery property such as a roll, when used in a roll state, for example, in a printing process for forming an image on a photographic printing paper after development, generation of scratches, focus, etc. Problems such as blurring and jamming at the time of conveyance will occur.

On the other hand, PET films have been considered to be an alternative to TAC because of their excellent productivity, mechanical strength, and dimensional stability. Since the habit curl remains strongly, the handleability after development processing is poor, and the range of use has been limited despite the excellent properties described above. P
For polyester polymers represented by ET,
Heat treatment at a temperature lower than the glass transition temperature (hereinafter, referred to as (Tg)) (hereinafter, Tg annealing, abbreviated as (BT)
A) is known (for example, US Pat. No. 4,141,735).
This is because when the film is wound on a roll, the polymer chains that easily flow and cause the curl curl are fixed in a state where they are stably arranged by thermal energy, and the heat treatment temperature This is a method of making it difficult to form curl under low temperature conditions. However, in the case of PET, since the Tg is as low as about 70 ° C., the film receives more heat history when using the film (for example, in a car under the scorching sun), and the molecular chains easily flow in a rolled state and are fixed. In some cases, the curl may show strong curl, and the effect of preventing curl by the BTA treatment is small.

However, a polymer having a Tg exceeding 80 ° C., for example, polyethylene naphthalate (hereinafter, referred to as (PEN), a Tg of about 120 ° C.) which is a polyester polymer similar to PET, or a polyarylate which is an amorphous polymer (Hereinafter referred to as (PA), Tg of about 190
C) or polycarbonate (hereinafter, referred to as (PC), Tg of about 150 ° C.) has a large curling prevention effect by the BTA treatment.

In recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transport during photographing, the increase in photographing magnification, and the miniaturization of photographing apparatuses have been remarkably progressing. In this case, the support of the photographic light-sensitive material is required to have properties such as strength, dimensional stability and thinning.

Further, with the downsizing of the photographing apparatus, the demand for downsizing the patrone has increased. Conventionally, 13
In the 5 system, a patrone having a diameter of 25 mm was used. However, if the thickness of this spool (core) was reduced to 10 mm or less and the thickness of the TAC support used in the current 135 system was reduced from 122 μm to 90 μm, the patrone could be used. The size can be reduced to 20 mm or less in diameter.

There are two problems in reducing the size of such a patrone. The first problem is a decrease in mechanical strength due to thinning of the film. In particular, the stiffness decreases in proportion to the cube of the thickness. A silver halide photographic light-sensitive material is generally provided with a light-sensitive layer dispersed in gelatin, and this layer causes shrinkage due to low humidity to generate a toy curl. The support must have enough stiffness to resist this contraction force.

The second problem is a strong curl that occurs during storage over time due to the miniaturization of the spool. Conventional 13
In the 5 system, the winding diameter is 14 mm even in the 35-sheet film having the smallest winding diameter inside the patrone.
If the size is reduced to 10 mm or less, a remarkable winding habit is formed, which causes various troubles. For example, when development processing is performed with a minilab automatic processor, the film is wound up because one end is fixed to the reader and the other end is not fixed, and the supply of the processing liquid is delayed, causing "processing unevenness". Cause. In addition, the winding of this film is crushed by the roller in the minilab,
"Breaking" occurs.

However, in the above-mentioned TAC, because of the nature of the rigid molecular structure, the film quality of the formed film is fragile and cannot be used for these applications, and the PET film has excellent mechanical properties. However, it has a problem that it cannot be used because of its strong curl. Also,
Polymers having a Tg of 80 ° C. or higher, particularly PEN, are expected to have excellent mechanical and thermal properties, etc., higher than PET and to be subjected to BTA treatment before being used for small photographic film applications. . However, it is an extremely important problem how to uniformly and quickly heat-treat a long-rolled film support after film formation. Heat treatment of the polyester film support, for the purpose of fixing the support in a flat state without curl,
It is most desirable to fix it by attaching it to a flat surface. However, this method is extremely disadvantageous in terms of production efficiency because it requires a planar plate having a huge area. Therefore, a method of winding around a core having a relatively large radius of curvature and performing heat treatment is generally used. In this case, what is problematic is the uniformity and rapidity of the heat treatment. Generally, the thermal conductivity of a polymer is smaller than that of a ceramic as well as a metal. For this reason, if it is attempted to heat the polyester film in a state of being thickly wound around the core, it takes an extremely long time until the inside is uniformly heated, and the productivity is extremely poor. However,
Conventionally, storage in such a state of being wound around a core has been considered, but treatment at such a high temperature for a long time has hardly been considered. Therefore, many types of cores conventionally used cannot withstand such a high-temperature heat treatment, resulting in deformation or non-uniform heat treatment due to the low thermal conductivity thereof, or In addition, since it has no function of heating from the inside of the core, it takes a remarkably long time to increase the temperature of the film near the core.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photographic light-sensitive material comprising a support having excellent mechanical properties and having less curl.

[0014]

In a photographic material having at least one photosensitive layer on a polyester film support, the polyester is a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main raw materials, The glass transition temperature is 90 ° C. or more and 200 ° C. or less, and between the film formation of the polyester film and the application of the photosensitive layer, the glass transition temperature of the polyester is 50 ° C. or more using a core that can be heated from the inside. This has been achieved by a photographic material characterized by using the polyester film support heat-treated at a temperature not higher than the temperature.

First, the curl measuring method used hereinafter and terms relating thereto will be described. (1) Core set The film is wound around the spool and rolled. (2) Core set curl The core set curl is applied in the length direction. The degree of curling is determined by the ANSI / ASC pH 1.29-1985 Te
It was measured according to st Method A and expressed as 1 / R [m] (R is the radius of the curl). (3) Absolute core set curl The core set curl of the photographic film before the winding improvement. (4) Controlled core set curl The core set curl of the photographic film after the curl improvement. (5) True core set curl The difference in curl of the photographic film before and after performing the core set processing. (6) Curl reduction rate [(absolute core set curl-controlled core set curl) / absolute core set curl] × 100 (7) Glass transition temperature (Tg) Using a differential scanning calorimeter (DSC), 10 mg of a sample film was used. When the temperature rises at 20 ° C./min in a nitrogen stream, the endothermic peak appears at the arithmetic mean temperature of the temperature at which the base line begins to deviate from the baseline and the temperature at which the temperature returns to the new pace line or at Tg. Is defined as Tg.

(8) Elastic Modulus A sample punched out into a dumbbell-type standard test piece with a mark interval of 50 mm using a tensile tester was stretched at a tensile speed of 10 mm / min. In the region where the strain and the corresponding stress show a linear relationship,
Obtain the slope of the stress with respect to the amount of strain. This is a value called Young's modulus, which is defined here as an elastic modulus. There are two ways to achieve the two issues described above: strong mechanical strength and low curl. The first method is a method in which TAC having curl recovery properties is modified to improve mechanical strength. The second method is a method of improving the mechanical strength so that the polyester support represented by PET is hardly curled. Achieving this task in the former way is expected to be very difficult. That is, the thickness of the TAC support used in the current color negative photographic material is 122 μm,
When the thickness is reduced to μm, the stiffness is proportional to the cube of the thickness, and therefore, is reduced to 40% of the 122 μm support. That is, it is necessary to achieve a support having a 2.5 times higher elastic modulus. Further, when the spool diameter is reduced to 10 mm or less, even the TAC having the winding recovery property cannot fully recover during the developing process, and the above-mentioned "processing unevenness" and "breaking" occur. As described above, it is considered to be quite difficult to simultaneously solve the two problems of “improving the elastic modulus by 2.5 times” and “improving the curl recovery”.

On the other hand, when the latter method is to be achieved, for example, a stiffness equivalent to 122 μm of TAC is required to be 90 μm due to the inherently high elastic modulus when PET is used.
m. Further, when PEN is used, the elastic modulus is higher than that of PET, and the thickness can be reduced to nearly 80 μm. Therefore, in the latter case, it is only necessary to improve the winding of these supports, and as a result of investigation, the present invention has been reached.

As described above, the winding of a film such as polyester can be improved by the BTA treatment. However, in order to achieve a sufficient effect, the film is usually heated to a desired temperature and then heated for 24 hours or more. Requires processing time. By the way, when manufacturing a polyester film, from the viewpoint of productivity, the width is usually 2 m or more and the length is several thousand m.
Is wound on one roll. When a BTA treatment is applied to such a long rolled film support, it is difficult to uniformly heat the inside because the thermal conductivity of the core and the polyester film is small. Therefore, in order to uniformly apply the BTA treatment to the inside of a roll film wound around a core as conventionally used, for example, when the roll film is placed in an air-heated thermostat at a desired temperature, at least It took five days. However,
According to the present invention, it has been found that when a core that can be heated from the inside is used as a core during BTA processing, the processing effect can be obtained very quickly and uniformly.

The core which can be heated from the inside in the present invention may have any structure and heating means, for example, a method of heating by flowing a heated fluid through a hollow structure. Any heating means such as a method of heating by passing a current through the dielectric may be used. Among them, from the viewpoints of cost, safety, and the like, a method of heating by passing hot water or steam through the hollow core is preferable. The material of the winding core may be any material as long as it has higher thermal conductivity than the film to be treated.However, from the viewpoint of mechanical strength, heat resistance, dimensional stability, etc., metal, ceramic, or ceramic coating is applied. Preferred metals are preferred.

Preferred examples of the metal include aluminum, stainless steel (indicating an alloy of iron, chromium, and nickel), brass (alloy of copper and nickel), copper, iron, and duralumin (containing copper, magnesium, manganese, and silicon). Alloy), more preferably aluminum, stainless steel, and iron. Also, as the ceramic material is not particularly limited, 3Al ₂ O ₃ -2S as preferred
_{iO 2, BaTiO 3, SrTiO 3} , Y 2 O 3 -Th
O ₂ , ZrTiO ₃ , ZrO ₂ , Si ₃ N, SiCMg
_{O · SiO 2, MgCr 2 O} 4 -TiO 2 can be mentioned, particularly preferred are, 3Al ₂ O ₃ -2Si
O ₂ , BaTiO ₃ , SiTiO ₃ , and ZrO ₂ .
The core of the present invention may be composed of a mixture or a laminate of two or more materials. For example, if the surface of aluminum is A
It may be coated with l ₂ O ₃ or with CrO ₂ . Alternatively, the surface of the stainless steel material may be coated with CrO ₂ , or in some cases, the surface may be coated with a very thin fluororesin. Next, the diameter (outer diameter) of the core of the present invention is 5 cm or more, and more preferably 7 cm to 2 cm.
m, more preferably 10 cm to 1.5 m, and particularly preferably 15 cm to 1 m.

The effect of curling curl reduction in the present invention was effective in polyester having a Tg of 90 ° C. or more and 200 ° C. or less. This is because the effect of this heat treatment is T
It is desirable to use a polyester having as high a Tg as possible, since it disappears when exposed to a temperature exceeding 90 ° C., which is 90 ° C. as a temperature exceeding the highest temperature when used by general users, that is, a temperature exceeding 80 ° C. in a car in summer. It is necessary to have the above Tg.

On the other hand, there is no general-purpose polyester film having transparency and a Tg exceeding 200 ° C. to date.
Therefore, the Tg of the polyester used in the present invention is 90
It is necessary to be higher than or equal to 200C and lower than or equal to 200C. There are various types of such polyesters, but polyester having naphthalenedicarboxylic acid and ethylene glycol as the main raw materials, which have high performance in balancing both the difficulty of winding and the mechanical strength, especially, Polyethylene-2,6-naphthalenedicarboxylate (PE
N). These supports are 50 μm or more and 300 μm or more.
It is necessary that the thickness be not more than μm. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying, while if it is more than 300 μm, it is inconsistent with the purpose of reducing the thickness for compactness.

This heat treatment must be performed at a temperature of 50 ° C. or more and Tg or less for 0.1 to 1500 hours. This effect proceeds faster as the heat treatment temperature is higher. However, when the heat treatment temperature exceeds Tg, the molecules in the film move in a random manner, and conversely, the free volume increases, and the film easily flows, that is, the film is easily rolled. Therefore, this heat treatment needs to be performed at Tg or less. On the other hand, at a temperature of 50 ° C. or less, this effect only proceeds at an extremely slow speed, so that it takes a lot of time and is impractical. Therefore, this heat treatment is desirably performed at a temperature slightly lower than Tg for the purpose of shortening the processing time, and is preferably 50 ° C. or higher and Tg or lower, more preferably 30 ° C. lower than Tg or higher and Tg or lower. On the other hand, when heat treatment is performed under these temperature conditions, an effect is recognized after 0.1 hour. On the other hand, after 1500 hours or more, the effect is almost saturated. Therefore, more than 0.1 hours
It is necessary to perform the heat treatment for 0 hour or less.

Hereinafter, the present invention will be described in more detail. However, the present invention is not limited by these. First, Tg used in the present invention is 90 ° C. or more and 20 ° C.
The polyester at 0 ° C. or lower will be described. The polyester according to the present invention, which is mainly composed of polyester naphthalenedicarboxylic acid having a glass transition temperature of 90 ° C. or higher and ethylene glycol.

[0025]

Embedded image

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

Among the polyesters comprising these diols and dicarboxylic acids, more preferred are polyethylene-2,6-dinaphthalate (PEN) and 2,6-naphthalenedicarboxylic acid (NDCA) as the dicarboxylic acid, and diols. As ethylene glycol (EG), cyclohexane dimethanol (CHDM),
Neopentyl glycol (NPG), bisphenol A
(BPA), biphenol (BP) and parahydroxybenzoic acid (PHBA) as a hydroxycarboxylic acid,
6-hydroxy-2-naphthalenecarboxylic acid (HNC
Those obtained by copolymerizing A) are mentioned. Among them, more preferred are 2,6-naphthalenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (the mixing molar ratio of naphthalenedicarboxylic acid and terephthalic acid is 0.3: 0.7 to 1.0: 0). Preferably between,
0.5: 0.5 to 0.8: 0.2 is more preferred. ),
Naphthalenedicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (neopentyl glycol and ethylene glycol have a molar ratio of 1: 0 to 0.7:
0.3 is preferable, and 0.9: 0.1 or more is more preferable.
0.6: 0.4) and PEN and PET
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable,
5: 0.5 to 0.8: 0.2 is more preferable).

PEN is the most balanced of these polyesters, has excellent mechanical strength, especially high elastic modulus, and has a sufficiently high glass transition temperature of around 120 ° C. However, it has the disadvantage of emitting fluorescence. On the other hand, PCT has high mechanical strength and a glass transition temperature of 110.
Although it is as high as around ° C., the crystallization rate is extremely high, and it has a drawback that a transparent film is hardly obtained. PAr has the highest glass transition temperature (190 ° C.) of these polymers, but has the disadvantage that the mechanical strength is weaker than PET.
Therefore, in order to make up for these drawbacks, it is possible to use a blend of these polymers or a copolymer of monomers forming them. These homopolymers and copolymers can be synthesized according to a conventionally known polyester production method. For example, when an acid component is directly esterified with a glycol component, or when a dialkyl ester is used as an acid component, first, a transesterification reaction is performed with the glycol component, and this is heated under reduced pressure to remove excess glycol components. By doing so, it can be synthesized. Alternatively, an acid component may be used as an acid halide and reacted with glycol. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used,
A heat stabilizer may be added. These polyester synthesis methods are described, for example, in Polymer Science Laboratory, Vol. 5, “Polycondensation and Polyaddition” (Kyoritsu Shuppan, 1980), p.
It can be carried out with reference to the description on page 36, pages 187 to 286 of "Synthetic Polymer V" (Asakura Shoten, 1971). The preferred average molecular weight range for these polyesters is from about 10,000 to 500,000.

The polymer blends of the polymers thus obtained are described in JP-A-49-5482 and JP-A-64-482.
4325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779
-82, 294, 807-14.

Next, preferred specific examples of the polyester used in the present invention will be shown, but the present invention is not limited thereto. Examples of polyester compounds ・ Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. Copolymer (() indicates a molar ratio. ) PBC-1 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C PBC-2 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C PBC-3 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C ・ Polymer blend (()) Represents a weight ratio.) PBB-1 PEN / PET (60/40) Tg = 95 ° C. PBB-2 PEN / PET (80/20) Tg = 104 ° C. PBB- 3 PAr / PEN (50/50) Tg = 142 ° C PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 ° C

An ultraviolet absorber may be kneaded into these polymer films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the amount thereof is usually 0.5% by weight to 20% by weight based on the weight of the polymer film.
% By weight, preferably about 1 to 10% by weight. If it is less than 0.5% by weight, the effect of suppressing the deterioration of ultraviolet rays cannot be expected. As the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4 Benzophenones such as 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;
(2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy3 ', 5'-di-t-
Benzotriazoles such as butylphenyl) benzotriazole and 2 (2'-hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole; and salicylic acid-based ultraviolet absorbers such as phenyl salicylate and methyl salicylate. Can be

One of the properties that may cause a problem when a polyester film is used as a support for a photographic light-sensitive material is a fogging problem that occurs because the support has a high refractive index. The refractive index of polyester, particularly aromatic polyester, is as high as 1.6 to 1.7, while the refractive index of gelatin, which is the main component of the photosensitive layer coated thereon, is 1.50 to 1.55. Less than this value. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester-based film causes a so-called light piping phenomenon (edge fogging). As a method of avoiding such a light piping phenomenon, a method of including inert inorganic particles in a film, a method of adding a dye, and the like are known. A preferred method of preventing light piping in the present invention is a method by adding a dye which does not significantly increase the film haze. The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general properties of the photosensitive material, and the dye has excellent heat resistance in the film forming temperature range of the polyester film, and polyester. Those having excellent compatibility with are preferred. From the above viewpoint, it is possible to achieve the object by mixing commercially available dyes for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary that the color density in the visible light range is measured with a color densitometer manufactured by Macbeth Co., and that it is at least 0.01. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be provided with lubricity according to the intended use, and the means for imparting lubricity is not particularly limited.
The kneading of an inert inorganic compound or the application of a surfactant is used as a general method. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC
O ₃ , talc, kaolin and the like are exemplified. In addition to the lubricity imparted by the external particle system in which inert particles are added to the polyester synthesis reaction system described above, a lubricity imparting method using an internal particle system in which a catalyst or the like to be added during the polymerization reaction of the polyester is precipitated can also be adopted. It is. Although there is no particular limitation on these means for imparting lubricity, transparency is an important requirement for the support for a photographic light-sensitive material. It is desirable to select SiO ₂ having a refractive index relatively close to that of the above or an internal particle system capable of relatively reducing the particle diameter to be precipitated. Further, in the case where lubricity is imparted by kneading, a method of laminating layers imparted with functions in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

Next, the heat treatment method for the polyester of the present invention will be described. The polyester of the present invention is wound around the core of the present invention at a temperature of 50 ° C. or higher and Tg or lower of the polyester, and the temperature is applied immediately after film formation or undercoating without cooling, without cooling. It is preferable to wrap at a temperature (50 ° C. or higher and Tg of polyester or lower). Furthermore, it is preferable that the winding core is previously heated to a temperature for heat treatment. At this time, the inside of the core is hollowed out so as to reach a predetermined temperature in a short time, and a heat medium (for example, hot water, steam, oil (for example, silicone oil,
Edible oil, mineral oil, etc.). By this method, cooling of the core after heating is easy, which is advantageous in manufacturing. It has been found that the polyester film wound up in this manner is hard to have a curl in a very short time by keeping the ambient temperature at a desired heat treatment temperature.

At this time, the thickness of the material of the present invention outside the core is not particularly limited as long as the polyester of the present invention can be used without deformation, but is preferably 2 mm or more, more preferably 5 mm or more. Particularly preferably, it is 1 cm or more. The polyester to be treated at a high temperature is wound into the core of the present invention, but the application width and application length are not particularly limited. Preferably the width is 0.1 to 1
0 m, more preferably 0.5 to 5 m, and still more preferably 1 to 5 m.

The coating length is preferably from 50 to 100.
00 m, more preferably 500 to 8000 m, even more preferably 1000 to 5000 m. When these polymer films are used for a support, since all of these polymer films have a hydrophobic surface, a photographic layer composed of a protective colloid mainly composed of gelatin (for example, a photosensitive silver halide emulsion layer) is provided on the support. , An intermediate layer, a filter layer, etc.) or a back layer having a weak hydrophobicity is very difficult to adhere firmly. Prior art attempts to overcome such difficulties include: (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment. A method of obtaining a bonding force by directly applying a photographic emulsion after performing a surface activation treatment such as a mixed acid treatment, an ozone oxidation treatment, and the like. (2) Once these surface treatments are performed, or without any surface treatment, There are two methods: a method in which an undercoat layer is provided and a photographic emulsion layer is coated thereon.

All of these surface treatments are thought to be due to the formation of polar groups on the originally hydrophobic support surface and to an increase in the crosslink density of the surface. It is considered that the affinity of the components contained in the undercoat solution with the polar group increases, or the fastness of the adhesive surface increases. Various modifications have been made to the structure of the undercoat layer, and a layer (hereinafter, abbreviated as the first undercoat layer) that adheres well to the support is provided as a first layer, and a second layer is formed thereon as a second layer. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter abbreviated as a second undercoat layer) that adheres well to a layer, and a single layer of applying only one resin layer containing both a hydrophobic group and a hydrophilic group. There is a law.

Among the surface treatments (1), the corona discharge treatment is the most well-known method, and any of the conventionally known methods, for example, JP-B-48-5043 and JP-B-47-5.
1905, JP-A-47-28067 and JP-A-49-83
No. 767, No. 51-41770, No. 51-13157
No. 6, etc. can be achieved.
The discharge frequency is 50 Hz to 5000 kHz, preferably 5 kHz
〜100 kHz is appropriate. If the discharge frequency is too low, stable discharge cannot be obtained, and pinholes occur in the object to be processed, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the price of the device, which is not preferable. Regarding the processing strength of the object to be treated, for improving the wettability of ordinary plastic films such as polyester and polyolefin, 0.0
An appropriate value is from 01 KV · A · min / m ^{2 to 5} KV · A · min / m ² , preferably from 0.01 KV · A · min / m ^{2 to 1} KV · A · min / m ² . The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm.

In many cases, glow discharge treatment, which is the most effective surface treatment, can be performed by any method known in the art, for example, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
Nos. 45-24040, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638, 3,309, No. 299, No. 3,424,735, No. 3,462,335, No. 3,475,307, No. 3,761,299, British Patent 997,093, JP-A-53-129262, etc. Can be used. Glow discharge treatment conditions are generally as follows:
rr, preferably 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow, sparks are likely to occur, it is dangerous, and there is a risk of destroying the workpiece. The discharge is generated by applying a high voltage between metal plates or metal rods arranged at one or more spaces in a vacuum tank. This voltage can take various values depending on the composition and pressure of the atmosphere gas.
A stable steady glow discharge occurs between Ｖ5000 V. A particularly preferred voltage range for improving adhesion is 2000
４4000V.

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

In the underlayer according to the present invention, SiO ₂ , Ti
O ₂ , inorganic fine particles such as a matting agent, or polymethyl methacrylate copolymer fine particles (1 to 10 μm) can be contained. In addition, various additives can be contained in the undercoat liquid as needed. Examples include surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first layer of the undercoat is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol in the undercoat liquid at all. However, if desired, the above-mentioned etching agent may be contained in the undercoat.

[0053]

[0054]

[0055]

The undercoat solution according to the present invention can be prepared by applying a well-known coating method such as a tip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or a method disclosed in US Pat. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 2,681,294. Optionally, U.S. Pat. No. 2,761,791
Nos. 3,508,947 and 2,941,898
No. 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by the method described in “Coating Engineering”, page 253 (1973, published by Asakura Shoten).

The binder for the back layer may be a hydrophobic polymer or a hydrophilic polymer as used for the underlayer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a lubricant, a matting agent, a surfactant, a dye, and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, for example, a carboxylic acid and a carboxylate as an anionic polymer electrolyte,
A polymer containing a sulfonic acid salt, for example, as disclosed in JP-A-48-220
No. 17, JP-B-46-24159, JP-A-51-30
No. 725, JP-A-51-129216 and JP-A-55-129216.
No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
No. 3, JP-A-48-91165, and JP-B-49-245.
No. 82, for example. Also, ionic surfactants are anionic and cationic, and are described in, for example, JP-A-49-85826 and JP-A-49-33630.
No., US 2,992,108, US 3,206,31
2, JP-A-48-87826, JP-B-49-1156
7, JP-B-49-11568, JP-A-55-708
No. 37 and the like.

Most preferred as an antistatic agent for the back layer
Things are ZnO, TiO_Three, SnO _Two, Al_TwoO_Three, I
n_TwoO_Three, SiO_Two, MgO, BaO, MoO_ThreeInside
At least one crystalline metal oxide selected from
Fine particles of these composite oxides. Used in the present invention
Fine particles of conductive crystalline oxide or its composite oxide
Its volume resistivity is 10⁷Ωcm or less, more preferably 10
^FiveΩcm or less. The particle size is 0.002 to
0.7μ, especially 0.005-0.3μ is desirable
New

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be any of black and white colors. Here, a color silver halide photographic material will be described. The light-sensitive material of the present invention only needs to have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There is no particular limitation on the number of layers and the order of the non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, the unit light-sensitive layer is The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layers are described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, and JP-A-61-113440.
The couplers and DIR compounds as described in the specifications of JP-A Nos. 1-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-1127.
No. 51, No. 62-200350, No. 62-20654
No. 1, No. 62-206543, No. 56-25738
No. 62-63936, No. 59-202264,
These are described in JP-B-55-34932 and JP-B-49-15495. Silver halide grains have crystal defects such as those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, and twin planes. Or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), 22-23,
"I. Emulsion preparation and types",
And No. 18716 (November 1979), 648
Page, "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chemie et Phisique Photograp)
hique, Paul Montel, 1967), Duffin Photographic Emulsion Chemistry, Focal Press (GF Duffin Photo
graphic Emulsion Chemistry (Focal Press, 196
6), "Manufacture and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making an
d Coating Photographic Emulsion, Focal Press, 19
64) and the like.

US Pat. Nos. 3,574,628;
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,43
It can be easily prepared by the methods described in 3,048, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. The additives used in such a process are Research Disclosure N
o. 17643 and No. 18716, and the relevant portions are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

(Types of Additives) (RD17643) (RD18716) 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, supersensitizer 23 to 24, page 648 right column Page 649 Right column 4 Brightener page 24 5 Antifoggants and stabilizers 24-25 Page 649 Right column 6 Light absorbers, filter dyes, UV absorbers 25-26 Page 649 Right column 650 pages Left column 7 Stain inhibitor page 25 right column page 650 left to right column 8 Dye image stabilizer page 25 9 hardener 26 page 651 left column 10 Binder 26 same as above 11 Plasticizer and lubricant 27 page 650 right column 12 Coating Auxiliaries and surfactants, pages 26 to 27, right column, page 650 In order to prevent the deterioration of photographic performance due to formaldehyde gas, it is described in U.S. Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound that can react with formaldehyde and be fixed to the light-sensitive material.

[0065]

[0066]

[0067]

[0068]

[0069]

The color photographic light-sensitive material according to the present invention is prepared according to the RD. Nos. 17643, pp. 28-29, and N
o. Development processing can be carried out by a usual method described in 18716, 615 left column to right column. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds disclosed in U.S. Pat. Nos. 3,342,597, 3,342,599, Research Disclosure 14,850 and 15,
No. 159, Schiff base type compounds;
No.

[0071]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 1) Preparation of Polyester Film For the polyester used for the support, PEN and PET pellets were dried under vacuum at 150 ° C. for 4 hours in advance, and then a biaxial kneading extruder was used at a mixing ratio shown in Table 1. 280
After kneading and extruding at ° C, the mixture was pelletized and adjusted. After the polymer pellets having various composition ratios prepared as described above were melt-extruded, they were sequentially stretched 3.4 times in the longitudinal direction and 4 times in the transverse direction to obtain a biaxially stretched film having a thickness of 80 μm.

[0072]

[Table 1]

2) Application of Undercoat Layer For each of Sample Nos. 1 to 16, both surfaces were irradiated with ultraviolet light, and then an undercoat solution having the following composition was applied.
After drying at 20 ° C. for 2 minutes, the film was wound. The coating amount was 10 cc / m ² . Gelatin 1 part by weight Water 1 酢 酸 Acetic acid 1 メ タ ノ ー ル Methanol 50 エ チ レ ン Ethylene dichloride 50 〃 p-chlorophenol 4 〃

3) Coating of Back Layer A back layer having the following composition was coated on one side of Sample Nos. 1 to 16 after the undercoating. 3-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were added to ethanol 300
It was dissolved in 0 parts by weight to obtain a homogeneous solution. To this solution was added dropwise a 1N aqueous solution of sodium hydroxide until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours,
A reddish brown colloidal precipitate was obtained. The reddish brown colloidal precipitate was separated by centrifugation. Add water to the precipitate and centrifuge to remove excess ions

Washing was carried out by separation. This operation was repeated three times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions had been removed were redispersed in 1500 parts by weight of water and sprayed into a baking furnace heated to 600 ° C. to give a bluish tin oxide-antimony oxide composite having an average particle size of 0.2 μm. Was obtained. The specific resistance of this fine particle powder is 25Ω
・ It was cm. A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and after coarse dispersion with a stirrer,
Horizontal sand mill (Product name: Dino Mill; WILLYA. BACHOFEN
(Manufactured by AG) and dispersed until the residence time became 30 minutes.

3-2) Preparation of Back Layer: Following Formula [A]
And dried at 130 ° C.
For 30 seconds. On this, the following coating liquid for coating layer (B) was further applied so as to have a dry film thickness of 0.1 μm.
Dry at 130 ° C. for 2 minutes. [Formulation A] The above conductive fine particle dispersion 10 parts by weight Gelatin 1 part by weight Water 27 parts by weight Methanol 60 parts by weight Resorcinol 2 parts by weight Polyoxyethylene nonylphenyl ether 0.01 parts by weight [Coating liquid for coating layer (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-chlorophenol 4 parts by weight

4) Heat treatment of the support After coating the undercoat layer and the back layer by the above method,
The heat treatment was performed under the following conditions. As comparative examples, those that were not subjected to heat treatment and those that were heated only in the surrounding atmosphere but were not heated inside the core were shown as comparative examples. The internal heating of the core was performed by passing hot water or superheated steam through the inside. All heat treatments were carried out with a core having a diameter of 30 cm and an undercoating surface wound outside. Among the mechanical strengths of these supports, the most important stiffness was measured with thinner supports. The stiffness was measured using a method called a ring method. That is, 35mm in width
In the sample slit in parallel to the length direction, the circumference is 10
A circular ring of cm was made and placed horizontally. This was 12 mm, and the load at the time of deformation was measured, which was used as a measure of stiffness. In this measurement, the measurement was performed so that the undercoat layer was the inner circumference of the ring, and the measurement was performed at 25 ° C. and 60% RH. Table 1 shows the measurement results. PEN has a stiffness of 80 μm, which is substantially equivalent to TAC of 122 μm. This value did not change even when the heat treatment of the present invention was performed.

5) Coating of Photosensitive Layer On the support (samples Nos. 1 to 16) obtained by the above method, layers having the following compositions were applied in a multi-layered manner to prepare a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0080]

Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.030 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Medium Speed Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, W-1 to W-3, B-4 to B- may be added to each layer to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium and rhodium salts.

[0095]

[Table 2]

In Table 2, (1) Emulsions A to F were prepared according to the examples in JP-A-2-19938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to F were prepared according to the examples in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin was used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

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6) Sample evaluation Photographic film samples No. 1 to No. 1 thus prepared
16 were evaluated for winding. The evaluation was performed according to the following procedure. 6-1) Core Set The sample film was slit to a width of 35 mm and a length of 1.2 m. This was humidified overnight at 25 ° C. and 60% RH, and then the photosensitive layer was wound inside and wound on an 8 mm spool. This was placed in a sealed container and heated at 80 ° C. for 2 hours to form a roll. This temperature condition is a condition assuming that the film was placed in the car in summer. 6-2) Development processing and curl measurement After the film wound under the above conditions was allowed to cool in a room at 25 ° C. overnight, a sample film was taken out from the sealed container, and was taken out of an automatic developing machine (Minilab FP). -550
B: Fuji Photo Film)
The curl was measured using a curl plate at 60% RH. The developing conditions are as follows.

Processing Step Temperature Time Color Development 38 ° C. 3 minutes Stop 38 ° C. 1 minute Rinse 38 ° C. 1 minute Bleach 38 ° C. 2 minutes Rinse 38 ° C. 1 minute Fix 38 ° C. 2 minutes Rinse 38 ° C. 1 minute Stabilizing bath 38 ° C. for 1 minute The treatment liquid used has the following composition. Color developing solution Caustic soda 2 g Sodium sulfite 2 g Potassium bromide 0.4 g Sodium chloride 1 g Eagle sand 4 g Hydroxylamine sulfate 2 g Ethylenediaminetetraacetic acid disodium dihydrate 2 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline / monosulfate) 4g Add water to total volume 1L Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70% aqueous solution) 30ml Acetic acid 30ml Sodium acetate 5g Potash alum 15g Add water to total volume 1L Bleaching solution Ethylenediamine Sodium iron (III) tetraacetate dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Folic acid 5 g Ammonia water Adjust pH to 5.0 Add water 1 liter in total Fixer Sodium thiosulfate 150 g Sodium sulfite 15 g Ho sand 1 g glacial acetic acid 15ml Potassium alum 20g Water to make the total amount 1 liter stabilizing bath Ho acid 5g sodium citrate 5g Metaho sodium (tetrahydrate) were added to 3g potassium alum 15g water total amount 1 liter

6-3) Results The results are summarized in Table 1. The following became clear from Table 1. According to the heating method of the present invention, using a core made of a material according to the present invention, a photographic film comprising a film support obtained by subjecting a film support to a BTA treatment by heating from the surrounding atmosphere and the inside of the core is 6 hours. In processing, curl curl can be significantly reduced,
No trouble occurred during development. On the other hand, although a core made of the material according to the present invention is used, the core is not heated from the inside of the core during the BTA processing, and the BTA processing is performed according to the heating method of the present invention. A photographic film composed of a film support without using a core made of a material could hardly reduce curl of curling, and caused problems such as uneven processing and breakage during development.

Example 2 1) Preparation of Photographic Film Terephthalic acid and 2,6-naphthalenedicarboxylic acid were used in various proportions as dicarboxylic acid components, ethylene glycol was used as a glycol component, and antimony trioxide was used as a catalyst at 0.025 mol% (acid To the components) to obtain a copolyester containing terephthalic acid and 2,6-naphthalenedicarboxylic acid at various ratios. The composition ratio of the dicarboxylic acid component of the copolymerized polyester and the intrinsic viscosity of the obtained polymer (unit: dl /
g) is shown below. The viscosity was measured at 30 ° C. with o-chlorophenol (1/1). Terephthalic acid / 2,6-naphthalenedicarboxylic acid [η] 12/88 0.76 22/78 0.79 50/50 0.73 72/28 0.75

After drying these copolyesters in the usual manner, each was melt-extruded at 290 ° C. to prepare an unstretched sheet, and then at 130 to 90 ° C., 3.5 times in the longitudinal direction, 135 to 95%. After successively stretching 3.7 times in the transverse direction at 200 ° C., heat-setting was performed at 200 ° C. for 5 seconds to obtain a 90 μm-thick 2
An axially stretched film was obtained. An undercoat layer and a back layer were applied to these film supports in the same manner as in Example 1. Thereafter, heat treatment was performed under the conditions shown in Table 3. Thereafter, the photosensitive layer was applied in the same manner as in Example 1 to obtain a photographic film sample (No. 1).
~ 16).

[0117]

[Table 3]

2) Sample evaluation Photographic film samples No. 1 to No. 1 thus prepared
For No. 16, evaluation of winding was performed in the same manner as in Example 1.

3) Results The results are summarized in Table 3. The following became clear from Table 3. According to the heating method of the present invention, using a core made of a material according to the present invention, a photographic film comprising a film support obtained by subjecting a film support to a BTA treatment by heating from the surrounding atmosphere and the inside of the core is 6 hours. In processing, curl curl can be significantly reduced,
No trouble occurred during development. On the other hand, although a core made of the material according to the present invention is used, the core is not heated from the inside of the core during the BTA processing, and the BTA processing is performed according to the heating method of the present invention. A photographic film composed of a film support without using a core made of a material could hardly reduce curl of curling, and caused problems such as uneven processing and breakage during development.

[0120]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is hardly curled and has strong mechanical properties.

Claims (6)

(57) [Claims] 1. A photographic material having at least one photosensitive layer on a polyester film support, wherein the polyester is a polyester mainly composed of naphthalenedicarboxylic acid and ethylene glycol, and has a glass transition temperature of Between 90 ° C. and 200 ° C. and between 50 ° C. and the glass transition temperature of the polyester between the film formation of the polyester film and the application of the photosensitive layer using a core heatable from the inside. A photographic light-sensitive material using the polyester film support heat-treated in step 1. 2. The material of the core is metal, ceramics,
2. The photographic material according to claim 1, wherein the material is a metal coated with a ceramic coating. 3. The photographic light-sensitive material according to claim 1, wherein the material of the core is aluminum, stainless steel, iron or ceramics. 4. The photographic light-sensitive material according to claim 1, wherein the structure of the core is hollow, and the core is heated by passing hot water or superheated steam therein. 5. The photographic material according to claim 1, wherein the photographic material is wound around a spool having a spool diameter of 10 mm or less. 6. The method according to claim 1, wherein the polyester is polyethylene-2,6.
6. The photographic material according to claim 1, wherein the photographic material is naphthalenedicarboxylate.