JPH0635117A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material excellent in dynamic characteristics and small in curling tendency by stretching a polyester film having a specified glass transition point with some temperature difference given between the front and reverse surfaces to form a support. CONSTITUTION:The silver halide photographic sensitive material has at least one photosensitive layer on the support made of a polyester film having a glass transition point of 90-200 deg.C, and this film is stretched before forming the support by giving some temperature difference between the front and reverse sides of the film. It is necessary to select naphthalene dicarboxylic acid and ethylene glycol as the main materials of the polyester, especially, to use polyethylene-2,6-naphthalene dicarboxylate (PEN) in order to obtain high performance as the support, and it is also necessary to treat the film at a temperature below the glass transition point by >=50 deg.C for 0. l-1500hr and to control the temperature difference at the time of stretching to be 10-100 deg.C.

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 particularly to a surface of 10 ° C. or more and 100 °
Halogen that is hard to curl with a polyester having a glass transition temperature of 90 ° C. or more and 200 ° C. or less that is heat-treated at a temperature of 50 ° C. or more and a glass transition temperature of the substrate or less The present invention relates to a silver halide photographic light-sensitive material.

[0002]

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, generally, 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 used. There is. Generally, as a photographic light-sensitive material, a film for X-ray,
A sheet-shaped film such as a plate-making film and a cut film, and a typical roll film are 35 m /
It is a color or black and white negative film that is stored in a cartridge with a width of m or less and is used by a general camera for shooting. TAC is mainly used as a support for a roll film, and the greatest feature of this is that it has no optical anisotropy and high transparency. Another feature is that it has excellent properties in decurling after development. That is, the characteristic of the molecular structure of the TAC film is that it has a relatively high water absorbency as a plastic film, so that curl curl that occurs over time in a situation of being wound as a roll film causes a molecular chain due to water absorption in the development process. The molecular chains that flow and become immobilized with the time of winding undergo rearrangement. As a result, it has an excellent property of eliminating curling curl once formed. In a photographic light-sensitive material using such a film that does not have curl curl recovery like TAC, when it is used in a roll state, for example, in a printing step of forming an image on photographic printing paper after development, etc. Problems such as occurrence of scratches, defocusing, and jamming during transportation will occur. On the other hand, PET film has been considered as an alternative to TAC because of its excellent productivity, mechanical strength, and dimensional stability. However, in the roll form widely used as a photographic light-sensitive material, curling curl Remains strong and the handling property after development is poor, and the range of use has been limited despite the excellent properties described above.

By the way, the use of photographic light-sensitive materials has been diversified in recent years, and the speed of film transport at the time of photographing, the increase of photographing magnification, and the downsizing of photographing apparatus have been remarkably advanced. In that case, as the support for the photographic light-sensitive material,
Properties such as strength, dimensional stability, and thinning are required. Further, with the downsizing of the photographing device, there is an increasing demand for downsizing of the cartridge. Conventionally, in the 135 system, a cartridge with a diameter of 25 mm has been used, but for example, this spool (core) is set to 10 mm or less, and at the same time, the current 135
If the thickness of the TAC support used in the system is reduced from 122 μm to 90 μm, the cartridge can be downsized to a diameter of 20 mm or less. In order to miniaturize such a cartridge, there are two problems. The first problem is a reduction in mechanical strength as the film becomes thinner. In particular, bending elasticity decreases in proportion to the cube of the thickness. A silver halide photographic light-sensitive material is generally coated with a light-sensitive layer dispersed in gelatin, and this layer causes shrinkage at low humidity to generate curl in the width direction (U-shape).
The support is required to have bending elasticity sufficient to withstand this contraction stress. The second problem is the strong curl that occurs during storage over time as the spool becomes smaller. In the conventional 135 system, the roll diameter is 14 mm even for the 36-shot film having the smallest roll diameter inside the cartridge. Attempting to reduce the size to 10 mm or less causes a marked curl, which causes various troubles. For example, when developing with a minilab automatic developing machine, one end is fixed to the reader and the other end is not fixed, so the film winds up, the supply of the processing liquid is delayed, and "processing unevenness" occurs. Cause. Also, the roll-up of this film is crushed by the rollers in the minilab, causing "folding".

[0004]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a photographic light-sensitive material having excellent mechanical properties and less curling.

[0005]

These problems are addressed in a silver halide photographic light-sensitive material comprising a polyester film support and at least one light-sensitive layer on which the glass transition temperature of the polyester film support is 90 ℃ or more 20
It is achieved by a silver halide photographic light-sensitive material characterized in that the temperature is 0 ° C. or lower and there is a stretching temperature difference between the front and back of the support when forming the polyester film support.

First, a description will be given of the winding curse measuring method used thereafter and terms and the like related thereto. (1) Core set To wrap the film around the spool and add a curl. (2) Core set curl A curl in the length direction attached by the core set. The degree of winding is Te of ANSI / ASC pH 1.29-1985.
It was measured according to st Method A and expressed in 1 / R [m] (R is the radius of the curl). (3) Absolute core set curl This is the core set curl of the photographic film before the curl is improved. (4) Controlled core set curl The core set curl of the photographic film after the curl has been improved. (5) True core set curl (Absolute core set curl)-(Controlled core set curl) (6) Curl reduction rate (True core set curl / Absolute core set curl) × 1
00 (7) Glass transition temperature (Tg) Using a differential thermal analyzer (DSC), sample film 10
When an endothermic peak appears at the arithmetic mean temperature or Tg of the temperature that begins to be biased from the baseline and the temperature that returns to the new paceline when mg is heated at 20 ° C / min in a helium-nitrogen stream, this The temperature shown at the maximum value of the endothermic peak is defined as Tg.

In order to achieve the above-mentioned two problems, that is, high mechanical strength and low curl, there are two methods. The first method is a method for modifying the TAC having a curl recovery property to improve the mechanical strength. The second method is
It is a method for improving the mechanical strength of a polyester support typified by PET so that it is difficult to curl. Achieving this task with the former method 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, and when it is reduced to 90 μm, the bending elastic modulus becomes
Since it is proportional to the cube of the thickness, it is reduced to 40% of the 122 μm support. That is, it is necessary to achieve a support having a modulus 2.5 times stronger. Further, when the spool diameter is reduced to 10 mm or less, even the TAC having the curl recovery property cannot be fully recovered during the development process, and the above-mentioned "processing unevenness" and "folding" occur. As described above, it is considered quite difficult to simultaneously solve the two problems of “improvement of elastic modulus 2.5 times” and “improvement of curl recovery”.

On the other hand, when the latter method is used, for example, the bending elasticity equivalent to TAC of 122 μm can be achieved at 90 μm because of the strong elastic modulus which PET originally has. In addition, polyethylene naphthalate (PE
N) has a higher elastic modulus than PET and is 80μ.
It can be thinned to near m. So in the latter case,
It is only necessary to improve the curling of these supports, and as a result of the study, the present invention was reached.

Several attempts have hitherto been made as methods for reducing the curl of a polyester film. For example, a method described in JP-A-51-16358, that is, a method of performing heat treatment at a temperature lower than the glass transition temperature by 30 ° C. to 5 ° C. is known. This method attempts to relax the enthalpy in the film during the heat treatment and reduce the free volume, thereby suppressing the flow of molecules and making it difficult to curl. When this method is used, it is necessary to carry out heat treatment at a temperature near the glass transition temperature for one day or more until a sufficient effect is exhibited, although an effect of making it difficult to curl up is recognized, and a great deal of time and energy are required. It had the drawback of

On the other hand, a method as disclosed in Japanese Patent Application Laid-Open No. 1-131550, that is, a structure is provided in the base so that a curl is formed in a direction opposite to a winding direction as a product,
There is a method of canceling out the curl that occurs during product storage.
In this method, in a sequential biaxial stretching step, a permanent curl is provided by imparting a difference in crystallinity and orientation by providing a temperature gradient on the front and back surfaces of the film between longitudinal stretching and transverse stretching. When using this method, when wound on a thin spool as the subject of the present invention,
It was not possible to obtain a sufficient winding curl improving effect.

However, a polyester film formed by giving a temperature difference at the time of stretching has a glass transition temperature of 50 or less.
When heat-treated at a temperature of ℃ or higher, a film with extremely low curl was obtained. This effect was effective for polyesters having a glass transition temperature of 90 ° C or higher and 200 ° C or lower. This is because the effect of this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so polyester with a glass transition temperature as high as possible is desirable, and the temperature exposed to the highest temperature when used by general users, that is, in summer It is necessary to have a glass transition temperature of 90 ° C. or higher as a temperature exceeding 80 ° C. in the car.

On the other hand, a general-purpose polyester film having transparency and having a temperature higher than 200 ° C. does not exist until now. Therefore, the temperature of the polyester used in the present invention needs to be 90 ° C. or higher and 200 ° C. or lower. There are various such polyesters, but it is a polyester having naphthalenedicarboxylic acid and ethylene glycol as the main raw materials, which has high performance by balancing both difficulty in winding and mechanical strength. It was polyethylene-2,6-naphthalenedicarboxylate (PEN). These supports need to have a thickness of 50 μm or more and 300 μm or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated at the time of drying, while if it is more than 300 μm, it contradicts the purpose of thinning the thickness for compactness.

This heat treatment must be carried out at a temperature of 50 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours. This effect progresses faster as the heat treatment temperature increases. However, when the heat treatment temperature exceeds the glass transition temperature, the molecules in the film move rather disorderly and conversely the free volume increases, and the molecules tend to flow, that is, the film is easily wound. Therefore, this heat treatment needs to be performed at a temperature not higher than the glass transition temperature. On the other hand, at a temperature of 50 ° C. or lower, this effect progresses only at a remarkably slow speed, which requires a lot of time and is impractical. Therefore, this heat treatment is desirably performed at a temperature slightly below the glass transition temperature for the purpose of shortening the treatment time, and is preferably 50 ° C. or higher and the glass transition temperature or lower, more preferably
The temperature is not less than 30 ° C. below the glass transition temperature and not more than the glass transition temperature. On the other hand, when performing heat treatment under these temperature conditions,
The effect is recognized after 0.1 hour. On the other hand, at 1500 hours or more, the effect is almost saturated. Therefore 0.1
It is necessary to perform heat treatment for not less than 1 hour and not more than 1500 hours.

The temperature difference during stretching is 10 ° C. or more and 10
It is necessary to be 0 ° C or lower. More preferably 1
It is desirable that the temperature difference be 0 ° C. or higher and 30 ° C. or lower. If the temperature difference is 10 ° C. or less, a sufficient structure difference cannot be provided on the front and back. The larger the temperature difference is, the larger the curl can be made. However, if a temperature difference of substantially 100 ° C. or more is attempted, a crystallization is too advanced to obtain a transparent film, or a film is formed. There arises a problem that the film cannot be stretched uniformly.

The present invention will be described in more detail below. However, the present invention is not limited to these. First, the glass transition temperature used in the present invention is 90.
A polyester having a temperature of not lower than 200 ° C and not higher than 200 ° C will be described. The polyester (B) having a glass transition temperature of 90 ° C. or more of the present invention is formed from a diol and a dicarboxylic acid, and usable dibasic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride and succinic acid. , Glutaric acid,
Adipic acid, sebacic acid, succinic anhydride, maleic acid,
Fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, diphenylene p,
p'-dicarboxylic acid, tetrachlorophthalic anhydride, 3,
6-endomethylene tetrahydrophthalic anhydride, 1,4
-Cyclohexanedicarboxylic acid,

[0016]

[Chemical 1]

[0017]

[Chemical 2]

And the like. Usable diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,7-heptane. Diol, 1,8-octanediol, 1,10-decanediol, 1,12-
Dodecanediol, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4
-Benzenedimethanol,

[0019]

[Chemical 3]

[0020]

[Chemical 4]

And the like. Further, if necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. In addition, the polyester of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or an ester thereof) at the same time in the molecule. Examples of such compounds include:

[0022]

[Chemical 5]

Among the polyesters composed of these diols and dicarboxylic acids, more preferred are polyethylene, 2,6-dinaphthalate (PEN), polyacrylate (PAr), polycyclohexanedimethanol terephthalate (PCT) and the like. Homopolymer and dicarboxylic acid 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), paraphenylenedicarboxylic acid (PPDC) ), As a diol, ethylene glycol (EG), cyclohexanedimethanol (CHD
M), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), and parahydroxybenzoic acid (PHB) as a hydroxycarboxylic acid.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) is copolymerized. More preferred among these are naphthalene dicarboxylic acid, terephthalic acid and ethylene glycol copolymers (mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 and 1.00, 0.
It is more preferably 5: 0.5 to 0.8: 0.2. ), A copolymer of terephthalic acid, ethylene glycol, and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, more preferably 0.5: 0.5). .About.0: 0.9), isophthalic acid, paraphenylenedicarboxylic acid, and a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0.1 when terephthalic acid is 1). 10.
0, 0.1 to 20.0, and more preferably 0.
2 to 5.0, preferably 0.2 to 10.0), naphthalene dicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.7: 0. 3 is preferable, and more preferably 0.9: 0.1 to 0.6: 0.
4) Copolymer of terephthalic acid, ethylene glycol and biphenol (The molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1: 0.9 to 0. 7: 0.3), a copolymer of para-hydroxybenzoic acid, ethylene glycol and terephthalic acid (molar ratio of para-hydroxybenzoic acid, ethylene glycol is 1: 0 to 0.1 :).
0.9 is preferable, and 0.9: 0.1 is more preferable.
0.2: 0.8) and other copolymers and PEN and PET
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable, and 0.
5: 0.5 to 0.8: 0.2 is more preferable), PET
And PAr (composition ratio of 0.6: 0.4 to 0: 1.0 is preferable, and 0.5: 0.5 to 0: 0.9 is more preferable).

PEN is the most balanced of these polyesters, has a mechanical strength, especially a high elastic modulus, and has a sufficiently high glass transition temperature of about 120 ° C.
However, it has the drawback of emitting fluorescence. On the other hand, P
CT has a high mechanical strength and a glass transition temperature as high as around 110 ° C., but has an extremely high crystallization rate, and has a drawback that it is difficult to obtain a transparent film. PAr has the highest glass transition temperature (190 ° C.) of these polymers, but has a drawback that mechanical strength is weaker than that of PET. Therefore, in order to make up for these drawbacks, blends of these polymers or copolymers of the monomers forming them can be used. These homopolymers and copolymers can be synthesized according to conventionally known polyester production methods. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, it can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, using a transesterification reaction, a catalyst or a polymerization reaction catalyst,
A heat resistance stabilizer may be added. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103 to 136, "Synthetic Polymer V" (Asakura Shoten, 1971). Year)
It can be performed with reference to the description on pages 187 to 286. The preferred average molecular weight range for these polyesters is about 10,000 to 500,000.

Polymer blends of the polymers thus obtained are disclosed in JP-A-49-5482 and 64-64.
4325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779.
-82, 294, 807-14, it can be easily formed. Further, in order to improve the adhesiveness with the polyester (A), the polyester (A) may be partially blended or the polyester (A) may be blended within a range not exceeding 90 ° C in order to improve the adhesion with the polyester (A). The monomer constituting (A) can be copolymerized, or the monomer having an unsaturated bond can be copolymerized in the polyester (B) and radically crosslinked.

Next, examples of preferable specific compounds of the polyester (B) used in the present invention are shown, but the present invention is not limited thereto. Polyester (B) compound example-Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C PCT: [terephthalic acid (TPA) / cyclohexanediene Methanol (CHDM) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Copolymer (() represents a molar ratio) PBC -12,6-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-4 TPA / EG / BPA (100 50/50) Tg = 105 ° C. PBC-5 TPA / EG / BPA (100/25/75) Tg = 135 ° C. PBC-6 TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. PBC-7 IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C. PBC-9 TPA / EG / BP (100/20/80) Tg = 115 ° C. PBC-10 PHBA / EG / TPA (200/100/100) Tg = 125 ° C. Polymer blend (() indicates 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) T = 142 ° C. PBB-4 PAr / PCT (50/50) Tg = 118 ° C. PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = All of the polyesters having a temperature of 108 ° C. or higher have a flexural modulus higher than that of TAC, and it is possible to realize the original purpose of thinning the film. However, PEN had the strongest bending elasticity among these, and when it was used, TAC was 1
It is possible to reduce the required film thickness of 22 μm to 80 μm.

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 added is usually 0.5% by weight to 20% by weight based on the weight of the polymer film.
%, 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. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4. Benzophenone-based compounds such as 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2
(2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy 3 ', 5'-di-t-
Examples include benzotriazole-based UV absorbers such as butylphenyl) benzotriazole, 2 (2′-hydroxy-3′-di-t-butyl-5′-methylphenyl) benzotriazole, salicylate-based UV absorbers such as phenyl salicylate and methyl salicylate. To be

Further, one of the properties which poses a problem when the polyester film is used as a support for a photographic light-sensitive material is a problem of fogging due to the high refractive index of the support. Polyesters, especially aromatic polyesters, have a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated thereon, has a refractive index of 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 film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that 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 property of the light-sensitive 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 preferable. From the above viewpoints, as the dye, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be imparted with slipperiness according to the use, and the slipperiness imparting means is not particularly limited.
The kneading of an inert inorganic compound or the coating of a surfactant is used as a general method. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC.
Examples are O ₃ , talc, kaolin and the like. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system described above, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material. Therefore, in the slipperiness imparting method means, a polyester film is used as an external particle system. It is desirable to select SiO ₂ having a refractive index relatively close to that, or an internal particle system capable of relatively reducing the precipitated particle size. Furthermore, in the case of imparting slipperiness by kneading, a method of laminating a layer imparted with a function 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, a film forming method in which a temperature difference between the front and the back is provided will be described. Specifically, for example, when the film is stretched at a specific ratio in the longitudinal direction after casting, an auxiliary heating means such as an infrared heater is provided on one side or both sides, and the curling curl is recovered after changing the stretching temperature on the front and back sides. Control incoming film curl. FIG. 1 shows a side view of a longitudinal stretching zone of a polyester film having a constitution according to the present invention. (FIG. 1) The film 1 after casting is heated by the longitudinal stretching rollers 2 and 3, and then is passed through a cooling roller 4 and sent to a transverse stretching zone (not shown). An infrared heater 5 is provided immediately after the stretching roller 3. With such a configuration, curl can be effectively controlled by setting the temperature difference between the front and the back immediately after the infrared heater to be in the range of 10 to 100 ° C, and more preferably 10 to 30 ° C. It is considered that the curl control mechanism in the present invention is caused by a difference in volumetric shrinkage in the heat treatment step when the crystallinity and orientation on the front and back of the film are different. That is, crystal growth easily occurs on the low temperature side rather than on the high temperature side, the density increases, and volume contraction occurs. Therefore, permanent curl with the low temperature side as the inner winding occurs. These differences can be analyzed by X-ray diffraction on the surface.

The film forming process is not particularly limited, but as a preferred example of the present invention, a case of sequential biaxial stretching in which the film is stretched at a specific ratio in the longitudinal direction after casting and further stretched in the lateral direction by a tenter will be described. In terms of process, crystallization occurs throughout the entire process from casting to stretching in the vertical and horizontal directions.Therefore, the step of imparting a difference in crystallinity between the front side and the back side is performed during casting, during vertical stretching, and during horizontal stretching. Alternatively, it may be set over a plurality of steps. During casting, it has the advantage that the thickness of the film is thickest and it is easy to make a difference in temperature between the front and back, but it causes microcrystals to grow under some conditions, making it unsuitable as a photographic support because of its optical and mechanical properties. However, there is a drawback that the crystal is broken during the stretching in the subsequent step and the curl cannot be controlled because the difference in the generated crystal appears as the difference in the isothermal crystallinity.
On the other hand, the difference in crystallinity that occurs in the stretching step appears as a difference in oriented crystallinity and is therefore less likely to be destroyed. Further, the stretching part is usually provided with heating and cooling means and an auxiliary heating means. Applying the method of the present invention is suitable in the stretching step because it is easy to add. Furthermore,
In the comparison between the longitudinal stretching process and the transverse stretching process, the latter has a film area several times larger, and thus the facility must be modified on a large scale. Therefore, in the above-described step of sequential biaxial stretching, it is optimal to give a difference in crystallinity between the front and back during longitudinal stretching.

When any of these polymer films is used as a support, since each of these polymer films has a hydrophobic surface, a photographic layer comprising a protective colloid mainly containing gelatin is formed on the support (for example, a light-sensitive halogenated photosensitive layer). It is very difficult to firmly bond (silver emulsion layer, intermediate layer, filter layer, etc.). The conventional techniques attempted to overcome such difficulties are (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 surface activation such as mixed acid treatment, ozone oxidation treatment, etc., and then directly applying a photographic emulsion to obtain the adhesive force, and (2) after these surface treatments once or without surface treatment, There are two methods: a method of providing an undercoat layer and a method of coating a photographic emulsion layer on the undercoat layer. (For example, US Pat. No. 2,69
8,241, 2,764,520, 2,86
4,755, 3,462,335, 3,47
5,193, 3,143,421, 3,50
1,301, 3,460,944, 3,67
4,531, British Patents 788,365, 80
No. 4,005, No. 891,469, Japanese Patent Publication No. 48-43
122, 51-446, etc.).

All of these surface treatments are considered to be caused by forming a polar group on the surface of the support which was originally hydrophobic, and increasing the crosslink density of the surface. As a result, It is considered that the affinity of the component contained in the undercoat liquid with the polar group is increased, or the fastness of the adhesive surface is increased. Also, various arrangements have been made for the composition of the undercoat layer, and a layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and the second layer is photographed as the second layer. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) that adheres well to a layer, and a single layer of applying a single resin layer containing both a hydrophobic group and a hydrophilic group There is a law.

Among the surface treatments of (1), the corona discharge treatment is the most well-known method, and any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043 and 47-5.
1905, JP-A-47-28067 and JP-A-49-83.
No. 767, No. 51-41770, No. 51-13157.
This can be achieved by the method disclosed in No. 6 or the like.
Discharge frequency is 50Hz ~ 5000kHz, preferably 5kHz
〜Several 100kHz is appropriate. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, 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 cost of the device, which is not preferable. Regarding the processing strength of the object to be treated, it is 0.0 in order to improve the wettability of ordinary plastic films such as polyester and polyolefin.
01 KV · A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.01 KV · A · min / m ^{2 to 1} KV · A · min / m ² is suitable. 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, the glow discharge treatment, which is the most effective surface treatment, is performed by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-2440, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638 and 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 No. 53-129262, etc. Can be used. The glow discharge treatment condition is generally a pressure of 0.005 to 20 To
rr, preferably 0.02 to 2 Torr is suitable. 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 and sparks will easily occur, which is dangerous and may damage the object to be treated. The electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage can take various values depending on the composition of the atmospheric gas and the pressure, but it is usually 500 within the above pressure range.
A stable steady-state glow discharge occurs between ~ 5000V. A particularly suitable voltage range for improving adhesion is 2000
~ 4000V.

The discharge frequency is from direct current to several thousand MHz, preferably 50 Hz, as seen in the prior art.
20MHz is suitable. Regarding the discharge treatment strength, 0.01 KV · A · min /
m ^{2 to 5} KV · A · minute / m ² , preferably 0.15 KV · A · minute / m ^{2 to 1} KV · A · minute / m ² .

Next, regarding the undercoating method (2), all of these methods have been well researched. For example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used for the first undercoating layer in the multi-layer method. A large number of polymers such as polyethyleneimine, epoxy resin, grafted gelatin, and nitrocellulose, including copolymers starting from monomers selected from the group consisting of itaconic acid, maleic anhydride, etc. Layers have been investigated for their properties primarily with respect to gelatin. In the single layer method, in many cases, good adhesion is achieved by swelling the support and interfacial mixing with the hydrophilic undercoat polymer. As the hydrophilic undercoat polymer used in the present invention, a water-soluble polymer, a cellulose ester,
Examples include latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch,
Examples thereof include polyvinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer, and examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable. As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol,
Examples thereof include m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred.

Various gelatin hardeners can be used in the subbing layer of the present invention. As a gelatin hardening agent, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on. The subbing layer of the present invention is S
Inorganic particles such as iO ₂ , TiO ₂ and matting agent or polymethylmethacrylate copolymer particles (1 to 10 μm)
m) can be included. In addition to this, the undercoat liquid may contain various additives as required. For example, 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 undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is generally well-known coating method, for example, tip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by the extrusion coating method using the hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 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 either a hydrophobic polymer or a hydrophilic polymer used in the subbing layer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, 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, and for example, as the anionic polymer electrolyte, carboxylic acid and carboxylic acid salt,
A polymer containing a sulfonate is disclosed in, for example, JP-A-48-220.
17, JP-B-46-24159, JP-A-51-30
725, JP-A-51-129216, JP-A-55-
It is a polymer as described in No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
3, JP-A-48-91165, JP-B-49-245.
No. 82 is available. Further, the ionic surfactant has anionic property and cationic property, and is disclosed in, for example, JP-A-49-85826 and JP-A-49-33630.
No., US2,992,108, US3,206,31
2, JP-A-48-87826, JP-B-49-1156
7, JP-B-49-11568, JP-A-55-708.
Compounds such as those described in No. 37 can be mentioned.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , SnO ₂ or Al _2.
O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO
It is fine particles of at least one crystalline metal oxide selected from the group ₃ or a composite oxide thereof. The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The particle size is 0.
It is desirable that the thickness is 01 to 0.7 μ, and particularly 0.02 to 0.5 μ.

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 light-sensitive material will be described. The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. The number of layers and the non-photosensitive layer and the order of the layers are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive 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, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the 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 the same color-sensitive layers. A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-43
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038 may contain the coupler, the DIR compound etc. which are described, and may contain the color mixing inhibitor so that it may be normally used. . A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,4.
70 or British Patent No. 923,045, JP-A-5
7-112751, 62-200350, 62
-206541, 62-206543, 56-
25738, 62-63936, 59-202.
No. 464, Japanese Patent Publication Nos. 55-34932, 49-154
No. 95. The silver halide grains are
Those with regular crystals such as cubes, octahedra and tetradecahedrons, those with irregular crystal shapes such as spheres and plates, those with crystal defects such as twin planes, or those It may be a composite type.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types",
And No. 18716 (November 1979), 648.
P. Glafkides, Chemie et Phisique Photograp, "Physics and Chemistry of Photography," by Graphide.
hique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin Photo
graphic Emulsion Chemistry (Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al., Making an
d Coating Photographic Emulsion, Focal Press, 19
64) and the like. U.S. Pat. Nos. 3,574,628 and 3,65
The monodisperse emulsions described in, for example, 5,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Pho
tographic Science and Engineering), Volume 14, 24
8-257 (1970); U.S. Pat. No. 4,434,434.
No. 226, No. 4,414, 310, No. 4,433, 0
48, 4,439,520 and British Patent No. 2,
It can be easily prepared by the method described in No. 112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such processes are Research Disclosure N
No. 17643 and No. 18716, the relevant parts 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.

(Type of Additive) (RD17643) (RD18716) 1 Chemical Sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to page 648, right column ~ Page 649 Right column 4 Whitening agent Page 24 5 Antifoggants and stabilizers 24 to 25 pages 649 Right column to 6 Light absorbers, filter dyes, UV absorbers 25 to 26 pages 649 Right column to 650 left columns 7 Anti-staining agent Page 25 Right column Page 650 Left-right column 8 Dye image stabilizer Page 25 9 Hardener 26 Page 651 Left column 10 Binder 26 Same as above 11 Plasticizers and lubricants Page 27 650 Right column 12 Coating Auxiliary agents, surface active agents, pages 26 to 27, page 650, right column Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, they are described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. . Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. issue,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
Those described in 511, 649, European Patent No. 249,473A, etc. are preferable. 5 for magenta coupler
-Pyrazolone-based and pyrazoloazole-based compounds are preferable, and U.S. Pat. Nos. 4,310,619 and 4,35.
1,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984).
June 60), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-72238, and JP-A-6-72238.
0-35730, 55-118034, 60-
185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in WO (PCT) 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,753,871, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Research Disclosure No. 1 is a colored coupler for correcting unwanted absorption of color forming dyes.
7643, Section VII-G, U.S. Pat. No. 4,163,670.
No. 57/39413, U.S. Pat. No. 4,000
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Examples of couplers in which the color forming dye has excessive diffusibility include U.S. Pat. No. 4,366,237 and British Patent 2,125,57.
No. 0, European Patent No. 96,570, and West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409,320.
U.S. Pat. No. 4,576,910, British Patent 2,102,13.
No. 7, etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
Patents described in D17643, VII to F, JP-A-5
7-151944, 57-154234, 60
Those described in U.S. Pat. No. 4,184,248, No. 63-37346, and U.S. Pat. No. 4,248,962 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, and JP-A-59-157638.
Nos. 59-170840 and No. 59-170840 are preferable.
Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427, US Pat. Nos. 4,283,472, and 4,338,393. No. 4,310,618 and the like, multiequivalent couplers, JP-A-60-185950.
No. 6, JP-A-62-24252 and the like, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DI.
R redox-releasing redox compounds, EP 17
No. 3,302A, a coupler that releases a dye that recovers color after separation, R.I. D. No. 11449, No. 24241, couplers releasing bleaching accelerators described in JP-A No. 61-201247, couplers releasing ligands described in US Pat. No. 4,553,477, JP-A-63-75747. Examples thereof include couplers that release the leuco dye described.
The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, and aniline derivatives. , Hydrocarbons and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less, and the film swelling speed T ¹ /
₂ is preferably 30 seconds or less. The film thickness is 25 ° C and relative humidity is 5
Means a film thickness measured at 5% tone humidity (2 days), the film swelling rate T _^1/2 can be measured in accordance with a known method in the art. For example, A Green (A. Gree
n) Photographic Science and
Engineering (Photogr. Sci. Eng.), Volume 19, 2
No., can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _^1/2 is 30 ° C. in a color developing solution, the maximum swollen film to reach when treated for 3 minutes 15 seconds 90% of the thickness and the saturation film thickness and time defined to reach the thickness of the T _^1/2. Film swelling rate T _^1/2 can be adjusted to gelatin as a binder by adding a hardening agent, or by changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, and N.
O. 18716, 615, can be developed by the usual method described in the left column to the 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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat. Nos. 3,342,597, indoaniline compounds, 3,342,599, Research Disclosures 14,850 and 15,
Schiff base type compound described in No. 159, No. 13,924
No.

[0051]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 After melt-extruding PET chips and PEN chips, they were stretched 3.4 times in the longitudinal direction and 4 times in the transverse direction to produce a biaxially stretched polyester film having a thickness of 80 μm. As shown, an infrared heater was installed as an auxiliary heating source on one surface of the longitudinal stretching zone (in this example, the surface contacting the casting drum during casting: hereinafter referred to as the CD surface). PEN has an extrusion temperature of 300
℃, longitudinal stretching temperature (CD side) 140 ℃, transverse stretching temperature 13
A film was formed at 0 ° C. and heat set at 250 ° C. for 6 seconds. On the other hand, PET has an extrusion temperature of 270 ° C., a longitudinal stretching temperature (CD surface side) of 100 ° C.,
A film was formed at a transverse stretching temperature of 110 ° C. and a heat setting of 220 ° C. for 6 seconds.
At the time of stretching, the voltage applied to the infrared heater was changed to form the supports A-1 to 8 and B-1 to 4 having different temperature differences between the front and back as shown in Tables 1 and 2.

[0052]

[Table 1]

[0053]

[Table 2]

The film thus formed tends to curl with the low temperature surface side as the inner winding surface.

2) Coating of Undercoat Layer Each of the supports A1 to 8 and B1 to 4 was subjected to corona discharge treatment on both sides thereof, and then an undercoat layer having the following composition was provided on the high temperature surface side during stretching. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during processing is 9.6 KHz, and the gap clearance between the electrode and the dielectric roll is 1.6 mm.
Met. Gelatin 3 g Distilled water 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g For Support C, an undercoat layer having the following composition was provided. Gelatin 0.2g Salicylic acid 0.1g Methanol 15cc Acetone 85cc Formaldehyde 0.01g

3) Coating of Back Layer A back layer having the following composition was coated on the surface opposite to the side on which the undercoat layers of the supports A1 to 8 and B1 to 4 after undercoating were provided. 3-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were added to 300 parts of ethanol.
It was dissolved in 0 part by weight to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The coprecipitate obtained is left at 50 ° C. for 24 hours,
A reddish brown colloidal precipitate was obtained. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. Do this operation 3
Excess ions were removed repeatedly. 200 parts by weight of the colloidal precipitate from which excess ions were removed was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish tin oxide-antimony oxide composite having an average particle size of 0.2 μm. Fine particle powder of The specific resistance of this fine powder is 2
It was 5 Ω · cm. 40 parts by weight of the fine particle powder and 60 parts of water
Part by weight of the mixed solution was adjusted to pH 7.0 and roughly dispersed with a stirrer, then a horizontal sand mill (trade name Dynomill; WILLYA. BACH
OFENAG) was dispersed and prepared until the residence time reached 30 minutes.

3-2) Preparation of back layer: the following formulation [A]
To a dry film thickness of 0.3 μm
And dried for 30 seconds. The following coating solution (B) for coating layer was further applied onto this so that the dry film thickness would be 0.1 μm,
It was dried at 130 ° C. for 2 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion described above 1 part by weight of gelatin 27 parts by weight of water 60 parts by weight of methanol 2 parts by weight of resorcin 0.01 part by weight of polyoxyethylene nonylphenyl ether [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 Support After coating an undercoat layer and a back layer by the above method, Table 1
The heat treatment was performed under the conditions shown in. All the heat treatments were carried out with the core having a diameter of 30 cm and the outer surface of the undercoat surface wound. In addition, as a comparative example, a sample not subjected to heat treatment was also prepared. Among the mechanical strengths of these supports, the most important bending elasticity was measured as the supports became thinner. The bending elastic modulus was measured by using a method called a ring method. That is, width 35mm
And the circumference of the sample is 10
A cm ring was made and placed horizontally. This was 12 mm, and the load at the time of deformation was measured and used as a measure of the bending elastic modulus. In this measurement, the undercoat layer was measured so that the undercoat layer was on the inner circumference of the ring, and the measurement environment was 25 ° C. and 60% RH. The results measured by these are shown in Table 1. PEN is 8
At 0 μm, a bending elastic modulus almost corresponding to TAC of 122 μm is shown. Further, this value did not change even when the heat treatment of the present invention was performed.

5) Coating of photosensitive layer On the support obtained by the above-mentioned method, each layer having the composition shown below is multilayer-coated to form a multilayer color photosensitive material A-1 to B-8.
~ 4 created. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per 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

[0061]

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 Sensitivity 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

6th 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 Sensitivity 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

10th 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

14th 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 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, each layer may be provided with W-1 to W-3, B-4 to B-. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0076]

[Table 3]

In Table 2, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0078]

[Chemical 6]

[0079]

[Chemical 7]

[0080]

[Chemical 8]

[0081]

[Chemical 9]

[0082]

[Chemical 10]

[0083]

[Chemical 11]

[0084]

[Chemical 12]

[0085]

[Chemical 13]

[0086]

[Chemical 14]

[0087]

[Chemical 15]

[0088]

[Chemical 16]

[0089]

[Chemical 17]

[0090]

[Chemical 18]

[0091]

[Chemical 19]

[0092]

[Chemical 20]

6) Sample Evaluation Photographic film samples A-1 to A-1 thus prepared
No. 8, B-1 to 4 were evaluated for curling. The evaluation was performed according to the following procedure. 6-1) Core set The sample film was slit into a width of 35 mm and a length of 1.2 m. After humidity-controlling this at 25 ° C. and 60% RH overnight, the photosensitive layer was wound inside and wound on an 8 mm spool as shown in Table 1. This was placed in a sealed container, heated at 80 ° C. for 2 hours and wound. This temperature condition is a condition assuming that the film was placed in the car in the summer. 6-2) Development processing and curl measurement After the film wound under the above conditions is left to cool in a room at 25 ° C overnight, a sample film is taken out from a hermetically sealed container, and this is processed by an automatic processor (Minilab FP). -550
B: manufactured by Fuji Photo Film Co., Ltd.) and immediately processed at 25 ° C
The curl was measured using a curl plate under 60% RH. The development processing conditions are as follows.

Treatment process Temperature Time Color development 38 ° C. 3 minutes Stop 38 ° C. 1 minute Water wash 38 ° C. 1 minute Bleach 38 ° C. 2 minutes Water wash 38 ° C. 1 minute Fixation 38 ° C. 2 minutes Water wash 38 ° C. 1 minute Stabilizing bath: 38 ° C. for 1 minute The treating solution used has the following composition. Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide 0.4g Sodium chloride 1g Hoh sand 4g Hydroxylamine sulfate 2g Ethylenediaminetetraacetic acid disodium dihydrate 2g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline monosulfate) 4g Water is added and the total amount is 1 liter Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70% aqueous solution) 30 ml Acetic acid 30 ml Sodium acetate 5 g Potassium alum 15 g Total amount 1 liter Bleach Liquid Ethylenediaminetetrairon (III) acetate sodium dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Folic acid 5 g Ammonia water Adjusting pH to 5.0 Total volume with water 1 liter Fixing solution Sodium thiosulfate 150 g Sodium sulfite -Soda 15g Ho sand 12g Glacial acetic acid 15ml Potassium alum 20g Water added to a total amount of 1 liter Stabilization bath Folic acid 5g Sodium citrate 5g Sodium metaphorate (tetrahydrate) 3g Potassium alum 15g Water added to a total amount 1 liter

6-3) Results The results are shown in Table 1. PEN having a glass transition temperature of more than 90 ° C is equivalent to a heat-treated product (A-5) of about 6 hours with a temperature difference during stretching (A-4) and 24 hours without a temperature difference (A-5). The curl reduction rate is shown. That is, the same result is obtained in 1/4 time. Further, when PEN is used, the bending elastic modulus by the circular ring method becomes 33 g, which is close to the value of 36 g at TAC 122 μm. Therefore, by using the PEN which has been subjected to the treatment of the present invention, there is an advantage that even if it is wound on a thin spool having a diameter of 8 mm, there is almost no winding mark which actually causes damage and the support can be thinned to 80 μm. On the other hand, when the heat treatment temperature exceeds Tg and reaches 125 ° C., the effect is almost lost as shown in A-6.
On the contrary, at 50 ° C. or lower, a large curl recovery effect was not observed even after the heat treatment for 1400 hours. (A-9)

If the temperature difference between the front and the back during stretching is less than 10 ° C., the curl reduction rate becomes insufficient as shown in A-3. Heat treatment time is 1650 at 110 ° C
Even if it was carried out for a time, it did not change so much as (A-7) and 6 hours (A-4), while almost no effect was obtained at 0.1 hours or less (A-8). On the other hand, in the case of PET having a glass transition temperature of 90 ° C. or lower, the curl is not reduced even if the heat treatment, the temperature difference at the time of stretching, and any combination thereof are used. Therefore,
The temperature difference between the front and the back during stretching is 10 ° C. or more and 100 ° C. or less, the glass transition temperature is 90 ° C. or more and 200 ° C. or less, the heat treatment temperature is 50 ° C. or more and Tg or less, and the heating time is 0.1 hour or more 150.
It should be 0 hours or less.

Example 2 1) Preparation of Sensitive Material Polyester used for the support is PEN, PET, PA.
r, PCT pellets were previously dried under vacuum at 150 ° C. for 4 hours, and then kneaded and extruded at 280 ° C. using a twin-screw kneading extruder at a mixing ratio shown in Tables 4 and 5 to prepare pellets. This polyester was formed into a film under the same stretching conditions as in PEN of Example 1. Table 3 shows the temperature difference between the front and back during the longitudinal stretching. This was further subjected to coating of an undercoat layer, coating of a back layer and heat treatment according to Example 1. The same method as in Example 1 was used to evaluate the flexural modulus using the circular ring method. Further, a photosensitive layer was applied according to Example 1 to prepare supports C-1 to C-16.

[0098]

[Table 4]

[0099]

[Table 5]

2) Evaluation of Sample The photographic film C1-16 thus prepared was evaluated for curl in the same manner as in Example 1. At the same time, sensitometric evaluation was carried out according to a conventional method to evaluate the fluorescence emitted from the support.

3) Results The results are shown in Tables 4 and 5. PEN / PET copolymerization system is C
-1 to 12 are shown. With respect to C-1 to C8 having Tg of 90 ° C. or higher, the effect of the present invention is exhibited, and only a 1/4 heat treatment eliminates a sufficient curl reduction rate and the development processing trouble associated therewith. PEN itself emits a slight amount of fluorescence, which has a practically acceptable level but affects the photographic sensitivity. P
When the blending ratio of EN is lowered, the fluorescence derived from the naphthalene ring of PEN decreases, and the fluorescence after C-3 has no problem at all. However, it has a drawback that the bending elastic modulus is lowered accordingly. On the other hand, when Tg is below 90 ° C, C-9 ~
As shown in 12, the effect of the present invention was not obtained. In addition, PAr / PCT-based polymer blend (C-13 to 1
In 6) as well, Tg exceeded 90 ° C., and the effect of the present invention was confirmed. As described above, regardless of the composition of the polyester,
If the Tg exceeds 90 ° C, the effect of the present invention can be obtained.

Example 3 1) Preparation of Sensitive Material For a polyester having a glass transition temperature of 90 ° C. or higher, a stainless steel autoclave was used, and dimethanol terephthalate and dimethanol 2,6-naphthalenedicarboxylic acid were used as dicarboxylic acids and ethylene was used as a diol. Glycol (EG), bisphenol A (BPA), and cyclohexanedimethanol (CHDM) were mixed in the compositions shown in Tables 6 and 7, and transesterification was carried out using 0.025 mol of antimony trioxide (based on the acid component) as a catalyst. Polycondensation was carried out by the method. The polyester synthesized in this manner was used in Example 1.
A film was formed by the same method as the PEN stretching conditions. Table 4 shows the temperature difference between the front and back during the longitudinal stretching. This was further subjected to undercoat layer coating, back layer coating, and heat treatment according to Example 1. In the same manner as in Example 1, the flexural modulus was evaluated by the ring method. A photosensitive layer was coated on this in accordance with Example 1 to obtain a photographic film sample D1-16.

2) Sample Evaluation Photographic film sample D1-1 thus prepared
For No. 6, the curl was evaluated in the same manner as in Example-1.

3) Results The results are shown in Table 4.

[0105]

[Table 6]

[0106]

[Table 7]

Examples of NDCA / TPA / EG copolymers D
1 to 12 are shown. D-1 to 8 have a Tg of more than 90 ° C., and by combining this with a temperature difference during stretching and heat treatment (D-3, 7), a sufficient curl reduction effect can be obtained in a short time. As a result, there was no trouble in the development process.
On the other hand, in D-9 to 12 in which the TPA content is further increased, Tg is lower than 90 ° C., so that there is no effect even if the temperature difference during stretching and heat treatment are applied. Also, TPA / EG / CHDM
Examples of / BPA system are shown in D-13 to 16, but Tg is 9
Since the temperature was higher than 0 ° C, a sufficient curl-up improving effect was obtained by carrying out the present invention. (D-15) As mentioned above,
By subjecting polyester having a glass transition temperature of 90 ° C. or higher to a temperature difference during stretching and a heat treatment at a glass transition temperature or lower,
Remarkably difficult to wind.

[0108]

By carrying out the present invention, it is possible to provide a silver halide photographic light-sensitive material which is hard to curl and has strong mechanical properties at the same time.

[Brief description of drawings]

FIG. 1 shows a side view of a longitudinal stretching zone according to the present invention.

[Explanation of symbols]

 1 ... Film 2, 3 ... Longitudinal stretching roller 4 ... Cooling roller 5 ... Infrared heater

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 1/93 // B29K 67:00

Claims (7)

[Claims] 1. A silver halide photographic light-sensitive material comprising a polyester film support and at least one photosensitive layer, wherein the polyester film support has a glass transition temperature of 90 ° C. or higher and 200 ° C. or lower, A silver halide photographic light-sensitive material characterized in that there is a stretching temperature difference between the front and back of the support when forming the polyester film support. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the stretching temperature difference between the front and back of the polyester support is 10 ° C. or more and 100 ° C. or less. 3. The polyester film support is 0.1 to 1 at a temperature of 50 ° C. or higher and a glass transition temperature of the polyester film support or lower between the undercoating and the coating of the photosensitive layer.
The silver halide photographic light-sensitive material according to claim 1 or 2, which has been heat-treated for 500 hours. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the polyester film support is composed of a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components. 5. The silver halide photographic light-sensitive material according to claim 1, wherein when forming a film with a drawing temperature difference between the front and back of the film support, it is carried out during the pre-drawing of the sequential drawing. material. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester film support has a thickness of 50 μm or more and 300 μm or less. 7. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester film support is polyethylene-2,6-naphthalenedicarboxylate.