JPH0643581A - Silver halide photographic sensitive material and its production - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material which is ameliorated in repelling and adhesion defect by transfer of a lubricant. CONSTITUTION:This silver halide photographic sensitive material is produced by forming at least one layer of photographic silver halide emulsion layers on at least one surface of a polyester film base, the glass transition temp. of which is >=90 deg.C and <=200 deg.C, and heat treating this polyester film at the temp. above 50 deg.C and below the glass transition temp. of the polyester film after the formation of the polyester film before application of photosensitive layers. After the Polyester film is heat treated at the temp. above 50 deg.C and below the glass transition temp. thereof, the surface of the base on the side opposite from the surface to be coated and provided with the silver halide emulsion layers is coated and provided with a slip layer.

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, which uses as a support a polyester having a glass transition temperature of 90 ° C. or more and 200 ° C. or less, which is heat-treated at a temperature of 50 ° C. or more and a glass transition temperature or less. The present invention relates to a silver halide photographic light-sensitive material that is hard to curl.

[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 winding diameter is the smallest in the cartridge 36
Even with a single film, the roll diameter is 14 mm. This is 10mm
If the following is attempted to reduce the size, there will be 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".

These problems have been solved in a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on at least one surface of a polyester film support, in which the polyester film support has a glass transition temperature. It is 90 ° C. or higher and 200 ° C. or lower, and the polyester film support is heat-treated at a temperature of 50 ° C. or higher and a glass transition point of the polyester film or lower between the film formation and the coating of the photosensitive layer. Was achieved by a silver halide photographic light-sensitive material.

In order to achieve the above-mentioned objects, the polyester film support has a film thickness of 5 times after the film formation and before the coating of the photosensitive layer.
The heat treatment is carried out at a temperature of 0 ° C. or higher and a glass transition temperature of the polyester film or lower, and an important problem is which stage of the heat treatment is performed. The polyester support manufacturing process includes casting, stretching, (winding), undercoating for adhering the photosensitive layer + coating of a layer on the opposite side of the photographic photosensitive layer (hereinafter referred to as undercoating step), winding, The steps of coating the silver halide photographic photosensitive layer are performed in that order, and the heat treatment step may be carried out by winding in a roll immediately after stretching or after the undercoating step and winding in a roll on a winding core. It is conceivable that during the undercoating step, the polyester film support may be heated to a temperature not lower than the glass transition point thereof by surface treatment and drying. Generally, it is wound up after the process.

By the way, on the surface of the silver halide photographic light-sensitive material opposite to the side having the photographic light-sensitive layer (hereinafter referred to as the back surface), the occurrence of scratches in the camera and the laboratory equipment is improved,
It is known to provide a sliding layer containing a sliding agent as the outermost layer in order to improve the deterioration of the driveability of the system. Examples of the slip agent include paraffin, Japanese Patent Publication No. 53-292,
Polyorganosiloxanes as disclosed in JP-B-59-4649 and JP-B-55-49294, higher fatty acid amides as disclosed in US Pat. No. 4,275,146, JP-B-58. -33541, British Patent No. 927,446, or Japanese Patent Laid-Open No.
Higher fatty acid esters (having 10 to 10 carbon atoms) as disclosed in JP-A Nos. 5-126238 and 58-90633.
(Esters of 24 fatty acids and alcohols having 10 to 24 carbon atoms), and higher fatty acid metal salts as disclosed in US Pat. No. 3,933,516, and JP-A-58-50534. Higher fatty acid-higher alcohol esters containing a branched alkyl group, such as those disclosed in Esters of linear higher fatty acids and linear higher alcohols, are known.

[0007]

However, when heat treatment is carried out in a roll state in the state where such a layer containing a lubricant is coated, the undercoat surface (the side on which the lubricant is coated with the photographic photosensitive layer ( Transfer to the undercoating surface), repelling at the time of coating the photosensitive layer, defective adhesion of the photosensitive layer, deterioration of the slipperiness of the back surface, and failure of white powder due to precipitation of the lubricant will occur. Therefore, it becomes a big problem in practical use. The object of the present invention is therefore to have excellent mechanical properties,
Further, the present invention provides a photographic light-sensitive material which has less curl, has no repelling and adhesion during coating of a photographic light-sensitive layer, has no white powder failure due to precipitation of a lubricant, and has excellent slipperiness.

[0008]

The object of the present invention is to have at least one photosensitive silver halide emulsion layer on at least one side of a polyester film support and have a glass transition temperature of 9 or less.
In a polyester film support having a temperature of 0 ° C. or higher and 200 ° C. or lower, after passing through a step requiring a glass transition point of the polyester support or higher during an undercoating step, it is wound in a step before applying a sliding layer, and a temperature of 50 ° C. or higher. The heat treatment was carried out at a temperature not higher than the glass transition point of the polyester film, and thereafter, at a temperature not higher than the glass transition point of the polyester, a silver halide photographic light-sensitive material coated with the remaining undercoat layer and sliding layer was solved.

First, a description will be given of the winding curse measuring method used hereinafter 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.

Next, a method for achieving the above-mentioned two problems, that is, strong mechanical strength and small curl will be described in detail. First, there are two ways to achieve these goals. The first method is a method for modifying the TAC having a curl recovery property to improve the mechanical strength. The second method is a method of improving the polyester support typified by PET, which is excellent in mechanical strength, so that it is hard to be curled. Achieving this task with the former method is expected to be very difficult. 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 flexural modulus is proportional to the cube of the thickness, and thus 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 a 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 122 μm of TAC can be achieved at 90 μm because of the strong elastic modulus inherent in the case of using PET. Furthermore, when polyethylene naphthalate (hereinafter referred to as PEN) is used, the elastic modulus is higher than that of PET and the thickness can be reduced to about 80 μm. Therefore, in the latter case, it is only necessary to improve the curling of these supports, and the present invention has been made by studying from this direction.

Several attempts have heretofore 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 Laid-Open No. 81-2269, that is, a structure is provided in the base so that curls are formed in the direction opposite to the winding direction of the product, and the diameter of the product is stored. There is a way to offset it with Karl. 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 this method is used, when it is wound on a thin spool as the subject of the present invention, it is not possible to obtain a sufficient curling improvement effect.

However, a polyester film formed by giving a temperature difference during 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, there is no general-purpose polyester film which is transparent and has a temperature higher than 200 ° C. 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 during drying, while if it is more than 300 μm, the effect of thinning it for compactness is completely lost.

The heat treatment is preferably 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 preferably performed at a temperature slightly below the glass transition temperature for the purpose of shortening the processing time, and is 50 ° C. or higher and the glass transition temperature or lower, and more preferably 30 ° C. or lower and the glass transition temperature or lower. It is the following. On the other hand, when the heat treatment is performed under this temperature condition, the effect is recognized after 0.1 hour. Meanwhile, 1500
Over time, the effect is almost saturated. Therefore, it is preferable to perform the heat treatment for 0.1 hour or more and 1500 hours or less.

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,

[0019]

[Chemical 2]

[0020]

[Chemical 3]

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,

[0022]

[Chemical 4]

[0023]

[Chemical 5]

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:

[0025]

[Chemical 6]

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, particularly a high elastic modulus, and has a glass transition temperature of about 120 ° C., which is sufficiently high.
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.

Example of Polyester (B) Compound Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. PCT: [terephthalic acid (TPA) / Cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Copolymer (() represents 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-4 TPA / EG / B PA (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) Tg = 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 / 5) Tg = 108 polyester as described above ℃ all have strong song modulus than TAC, it is possible to realize a thinning of the film is the original purpose. 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 providing stability over 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 a 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 depending on 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, the case of successive biaxial stretching in which the film is stretched at a specific ratio in the longitudinal direction after casting and then in the transverse 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.

Next, the undercoating process for the polyester film support of the present invention will be described in detail. When the polyester film is used as a support, since each of these polyester films has a hydrophobic surface, a photographic layer comprising a protective colloid mainly containing gelatin on the support (for example, a photosensitive silver halide emulsion layer, It is very difficult to firmly bond an intermediate layer, a filter layer, etc.) or a back layer having weak hydrophobicity. The conventional techniques attempted to overcome such difficulties include (1)
Direct photo after surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc. There are two methods: a method of applying an emulsion to obtain adhesive strength, and (2) a method of applying a photographic emulsion layer on the undercoat layer after surface treatment of these or without surface treatment. is there. (For example, US Pat. Nos. 2,698,241 and 2,764,520.
Issue 2, Issue 2,864,755, Issue 3,462,335
Issue No. 3,475,193 Issue 3,143,421
Issue No. 3,501,301 Issue No. 3,460,944
No. 3,674,531, British Patent No. 788,36
5, No. 804,005, No. 891,469, Japanese Patent Publication No. 48-43122, No. 51-446, etc.).

All of these surface treatments are considered to be caused by forming polar groups on the surface of the support, which was originally hydrophobic, to some extent, 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), 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 DC 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 . UV treatment which is particularly preferable as a pretreatment for the organic solvent-based undercoating is carried out by any conventionally known method, for example, Japanese Patent Application No. 39-14534.
No. 39-16094, Japanese Patent Publication No. 45-3828 and the like can be used.

The UV irradiation conditions will be described in more detail. That is, this method is a method in which the above-mentioned ultraviolet irradiation is performed during the film forming step, and is preferably a method in the latter half of the stretching step or during heat setting. According to this method, since ultraviolet irradiation can be performed at a high temperature in the range of 90 ° to 250 ° C, it is possible to improve the efficiency of irradiation, and in comparison with the case where irradiation is performed after the film formation is completed, ultraviolet irradiation Since it is not necessary for the film support to pass through the inside of the high temperature apparatus for the purpose, it is also advantageous in improving the thermal efficiency and shortening the manufacturing process. The above-mentioned ultraviolet irradiation is carried out during the stretching step and heat setting, and particularly when carried out at the time of heat setting, 150 ° C to 250 ° C.
Since irradiation is performed at a high temperature of ℃, compared with irradiation after heat setting, the intended purpose can be achieved with an irradiation time of 1/2 to 2/3.
It is especially advantageous. Although it is advantageous in that the length of the mercury lamp may be short when UV irradiation is performed before or during the stretching, the temperature is limited to a relatively low temperature, so that the treatment efficiency is high. It is inferior to the case of irradiation during heat setting.

A more specific description will be given by taking an example of the film-forming undercoating process of the photographic film support.
The film support melted at a temperature of 290 ° C. to 300 ° C. and extruded onto the cooling drum is then lengthwise 2. while passing through a hot roll heated to a temperature of 85 ° C. to 90 ° C.
It is stretched 5 to 3.3 times. Next, this support is fed to a film-forming and irradiation device, which is shown in FIG. 2, and is composed of a frame edge having a chain of chains arranged in a chain on both sides, and a state in which both ears are bitten in sequence. 2.5 in the temperature range of 95 ℃ to 110 ℃ in the width direction.
˜3.3 times stretched, then heat set at a temperature of 210 ° C. to 230 ° C. This stretching device is roughly divided into three blocks. That is, it is divided into a 1.9 m preheated transverse stretching zone, a 2.6 m heat setting, an irradiation zone and a 3.4 m cooling zone in FIG. 2, and a 1 m wide film support of 15 m / min is used in this device. Processed at speed. The ultraviolet irradiation device is as follows. That is, 12 3KW high-pressure mercury lamps consisting of a quartz tube with an effective arc length of about 1 m are installed in the heat setting zone at intervals of 1 m (9 in Fig. 2), and each mercury lamp is 0.3 m from the film surface. The lamps are arranged in parallel with each other and each lamp is provided with a chrome-plated reflector (10 in FIG. 2) to improve the irradiation efficiency. When exposed to UV light, the film is sandwiched between the ears at all times, and is continuously processed while maintaining the tension during heat shrinkage, giving it a very smooth surface. . In FIG. 2, 11 is exhausted air, 12 is hot air, 13 is cold air, 14 is a fastening frame, and 15 is winding. In a suitable step after the cooling zone on the surface of the film support thus irradiated with radiation (if necessary, another precoater is used after winding), the solvent or swelling agent of the polyester is 1 to 25% ( By coating a hydrophilic resin solution or a gelatin dispersion liquid containing a mixed organic solvent (weight percentage), a film support having excellent adhesion to gelatin and a silver halide photographic emulsion is completed. In the undercoat liquid used here, in addition to organic solvents, additives for the purpose of reinforcing the undercoat layer, improving the adhesiveness to the support or emulsion layer, antistatic, or for coloring the support, that is, Further, a hardening agent, an antistatic agent, a dye and the like may be added. In some cases, by adding a hardening agent such as an ethyleneimine derivative or an epoxy derivative to the undercoating liquid, the desired adhesiveness may be obtained even by irradiation with ultraviolet rays for a shorter time than when not added. Ultraviolet rays which are particularly useful in the present invention are ultraviolet rays having a wavelength of 3200 to 2200Å.

Next, regarding the undercoating method (2), all of these methods have been well studied, and 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.

Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. 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. As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-
Examples thereof include 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 hardeners can be used in the subbing layer of the present invention. Gelatin hardening agents include chromium salts (chrome alum, etc.), aldehydes (formaldehyde,
Glutaraldehyde, etc., isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-
S-triazine, etc.), epichlorohydrin resin and the like. The subbing layer of the present invention comprises SiO ₂ ,
Inorganic particles such as TiO ₂ and a matting agent or polymethylmethacrylate copolymer particles (1 to 10 μm) can be contained. 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. Further, the organic solvent-based undercoat will be described in detail. First, the multilayer undercoat will be described. The hydrophobic binder for the first layer is preferably one having an affinity for PET, and the solubility parameter is mentioned as a selection criterion. Actually, there are amorphous polyester, vinyl chloride / vinyl acetate copolymer, polyvinyl acetal, nitrocellulose and the like. The second layer is often a dispersion of gelatin in an organic solvent.

Next, the single-layer undercoat will be described. This system is a system in which a hydrophilic binder is directly applied to PET and adhered thereto. The binder may be a dispersion of gelatin in an organic solvent or a dispersion of gelatin and nitrocellulose. However, in this system, it is necessary to apply a PET swelling agent at the same time, anchor the binder into PET, and physically anchor it to PET.

The hydrophilic binder used in the present invention includes —OH, —COOH, O = (CO) ₂ on the side chain.
=, - SO ₃ M (M is H or an alkali metal) -NH _2,
Cyclic amide, -COR ₁ R ₂ (R ₁ and R ₂ are H or C = 4
Synthetic polymer compounds soluble in organic solvents and swelling or dissolving in water, including the above alkyl groups) or heterocyclic groups containing nitrogen, etc., or equivalent to two or more kinds: eg, cellulose acetate phthalate, cellulose acetate Maleates, vinyl copolymers containing maleic anhydride, for example vinyl acetate and maleic anhydride (1: 1) copolymer (see German Patent No. 1040898 if necessary), polyvinyl alcohol containing SO ₃ M groups. Many hydrophilic resins such as acetal compounds (see British Patent No. 894,509), mixed acetals containing -COOM groups of polyvinyl alcohol or partial esterification products of divalent acids, and mixtures of polyvinylpyrrolidone and polyacrylic acid can be mentioned. . Instead of the hydrophilic binder solution described above, an undercoat liquid composed of a gelatin dispersion liquid may be used.

As the solvent or swelling agent for the polyester used in the present invention, for example, a ketone or an aldehyde containing an aromatic or partially saturated aromatic group and an aldehyde having a heterocyclic group containing nitrogen (UK Patent No. 772600) are used. No.), the general formula R-COOH or R
A carboxylic acid represented by -X-COOH or an anhydride thereof, an ester, an amide or a nitrile obtained from the acid, wherein R is aromatic or an aromatic heterocyclic compound containing nitrogen in the ring, and X is- CH ₂ or -OCH ₂
(See British Patent No. 777157), aliphatic monohydric alcohols or amines containing aromatic groups (see British Patent No. 785789), alcohols, ketones, carboxylic acids and their substituents or their esters (United Kingdom). Patent No. 797425), -NO ₂ to the aromatic nucleus, benzyl alcohol replacing -Cl (US Patent No. 2,830,030), chloral hydrate (German Patent No. 1020457), pyrrole (German Patent No. 1,092,652) and the like There, as specific examples of the above-mentioned solvent, benzoic acid, salicylic acid, salicylic acid ester, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-nitropropanol, benzyl alcohol, benzaldehyde, acetonylacetone. , Acetophenone, ben Amide, benzonitrile, benzylamine, methyl nicotinate and the like. Besides this,
Known polyester solvents or swelling agents include phenol, orthochlorophenol, cresol and other phenol derivatives.

The organic solvent used in the present invention must contain 1 to 25% (weight percentage) of the polyester solvent or swelling agent as exemplified above in the undercoating liquid component. If it is 25% or more, the flatness of the finished film is often significantly impaired, and if it is 1% or less, the desired effect is scarce. The addition amount of the polyester solvent or swelling agent can be changed depending on the type of the polyester solvent or the swelling agent and the type of other coexisting organic solvent, in addition to the polyester film support used and the irradiation conditions thereof. As a matter of course, two or more kinds of polyester solvents or swelling agents may be mixed and used at the same time. In this case, the added amount is
The total amount of the mixed polyester solvent or swelling agent is 1 to 25% of the total organic solvent. 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. No. 2,681. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 294,294. If desired, US Pat. Nos. 2,761,791 and 3,508,947
Nos. 2,941,898, and 3,526,52
No.8, Yuji Harasaki, "Coating Engineering" 253
Two or more layers can be simultaneously coated by the method described in page (1973, published by Asakura Shoten).

In the undercoating process as described above, surface treatment, use of a solvent having a high boiling point, an etching agent, and a cross-linking agent for providing adhesion are used, so that a high temperature is often required in the drying process. However, there is a high possibility that the temperature will be higher than the glass transition point of the polyester film support. In this case, the effect of improving the curl of the support is lost. Therefore, in the undercoat, after finishing the steps requiring a glass transition temperature of the support or higher, heat treatment below the glass transition temperature of the support is performed, and the remaining layers are below the glass transition temperature of the support and It is desirable to apply.

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 agents for the back layer are ZnO, TiO ₃ , SnO ₂ , Al ₂ O ₃ and I.
It is fine particles of at least one crystalline metal oxide selected from n ₂ O ₃ , SiO ₂ , MgO, BaO and MoO 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 ⁷ Ωcm or less.
⁵ Ωcm or less. The particle size is 0.002-0.7.
It is desirable that the thickness is μ, particularly 0.005 to 0.3 μ.

Next, the sliding layer used in the present invention will be described in detail. The slipping agent contained in the slipping layer in the present invention is at least one selected from organopolysiloxane, higher fatty acid and its derivative, higher alcohol and its derivative, and paraffin, which are generally used as a material for imparting slipperiness. It is a slip agent. Of these, polyorganosiloxane is generally known,
In addition to polyalkyl siloxanes such as polydimethyl siloxane polydiethyl siloxane, poly diaryl siloxanes such as polydiphenyl siloxane, and polymethyl phenyl siloxane, Japanese Patent Publication No. 53-292 and Japanese Patent Publication No. 55-49.
No. 294, JP-A-60-140341, etc., an organopolysiloxane having a C5 or more alkyl group, an alkylpolysiloxane having a polyoxyalkylene group in a side chain, an alkoxy, hydroxy, hydrogen in a side chain, A modified polysiloxane such as an organopolysiloxane having a carboxyl group, an amino group or a mercapto group may be used, or a block copolymer having a siloxane unit or a siloxane unit as disclosed in JP-A-60-191240 may be used as a side chain. It is also possible to use a graft copolymer having Specific examples of such compounds are shown below, but the present invention is not limited thereto.

[0055]

[Chemical 7]

The higher fatty acids and their derivatives, the higher alcohols and their derivatives include higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid polyhydric alcohol esters, and higher aliphatic compounds. Alcohol, higher alkyl alcohol monoalkyl phosphite, dialkyl phosphite, trialkyl phosphite, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, amide compound or salt thereof, etc. Can be used. Also,
Among them, the more preferable one is from the following general formula (1)
It is a slip agent as shown in (4).

[0057]

[Chemical 8]

In the formula, R ₁₁ represents a linear aliphatic hydrocarbon group having 11 or more carbon atoms, and R ₁₂ represents a linear aliphatic hydrocarbon group having 25 or more carbon atoms. R ₁₃ and R ₁₄ each have 12 carbon atoms
The above aliphatic hydrocarbon groups are represented, and either R ₁₃ or R ₁₄ represents a branched aliphatic hydrocarbon group. Also, R ₁₃ and R ₁₄
Has a total carbon number of 32 or more. In addition, R ₁₅ , R ₁₆ , R ₁₇ ,
R ₁₈ and R ₁₉ represent a linear or branched aliphatic hydrocarbon group having 12 or more carbon atoms, and X represents a divalent linking group. Specific examples of such compounds are shown below, but the present invention is not limited thereto.

[0059]

[Chemical 9]

By using such a slipping agent, the scratch resistance is excellent, and repelling on the undercoat surface does not occur,
A silver halide photographic light-sensitive material whose slipperiness is not deteriorated can be obtained by developing the photographic light-sensitive material. The amount of the slip agent used in the present invention is not particularly limited, but its content is 0.000.
5 to 2 g / m ² is preferable, more preferably 0.001
To 1 g / m ² , particularly preferably 0.002 to 0.5 g / m ²
Is. The layer to which the slip agent of the present invention is added is not particularly limited to this, but it is preferably contained in the outermost layer on the back surface.

The surface layer containing the above-mentioned slipping agent is obtained by coating a coating solution prepared by dissolving this in an appropriate organic solvent on a support or a support having a back layer on which other layers are applied, and then drying. Can be formed. The slip agent can also be added to the coating solution in the form of a dispersion. Examples of the solvent used include water, alcohols (methanol, ethanol, isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, etc.). Methyl, ethyl, propyl, butyl ester, etc.), hydrocarbon type (hexane, cyclohexane, etc.),
Halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, toluene, xylene, benzyl alcohol, benzoic acid, anisole, etc.), amides (dimethylformamide, dimethylacetamide, n-) Methylpyrrolidone etc.), ether type (diethyl ether), dioxane,
Tetrahydrofuran etc.), ether alcohols such as propylene glycol monomethyl ether, glycerin, diethylene glycol, dimethyl sulfoxide and the like are preferable.

In coating the above-mentioned slip agent, it is possible to use it together with a binder capable of forming a film. As such a polymer, a known thermoplastic resin, thermosetting resin, radiation curable resin, reactive resin, a mixture thereof, or a hydrophilic binder such as gelatin can be used. Examples of the thermoplastic resin include cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyacetyl cellulose phthalate, cellulose long chain alkyl ester, nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate resin. Cellulose derivative, vinyl chloride
Vinyl acetate copolymer, vinyl chloride, vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl acetate copolymer Vinyl-based copolymers such as polymers, acrylic resins,
Polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, silicone resin, Fluorine-based resins may be mentioned.

As the radiation curable resin, the above-mentioned thermoplastic resin to which a group having a carbon-carbon unsaturated bond is bonded as a radiation curable functional group is used. Preferred functional groups include an acryloyl group and a methacryloyl group. In the above-listed binding molecules, polar groups (epoxy group, CO ₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M, O
SO ₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , provided that M is hydrogen, alkali metal or ammonium, and when there are a plurality of Ms in one group, they may be different from each other.
R is hydrogen or an alkyl group. ) May be introduced. The polymer binders listed above may be used alone or as a mixture of several kinds, and a known isocyanate-based crosslinking agent and / or a radiation-curable vinyl-based monomer may be added for curing treatment.

The hydrophilic binders are described in Research Disclosure No. 17643, page 26, and No. 18716, page 651, and include water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters and the like. It is illustrated. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like, and cellulose ester includes carboxymethyl cellulose and hydroxyethyl cellulose. Is. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene anhydride-containing copolymers, acrylic ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Of these, gelatin is more preferable. Further, a gelatin derivative or the like may be used in combination with gelatin. The protective layer containing gelatin can be hardened. Examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1, 3,5-triazine,
In addition, compounds having reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, compounds having reactive olefin, N-hydroxymethylphthalimide, N Mention may be made of methylol compounds, isocyanates, aziridine compounds, acid derivatives, epoxy compounds, halogen carboxaldehydes such as mucochloric acid. Alternatively, examples of the inorganic compound hardening agent include chrome name van, zirconium sulfate and the like. Also,
A carboxyl group-activating type hardener can also be used. In the application of the above-mentioned sliding layer, it is desirable that the drying condition is carried out below the glass transition point of the polyester support.

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 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.

(Types of Additives) (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 Page 9 Hardener 26 Page 651 Left column 10 Binder 26 Same as above 11 Plasticizers and lubricants Page 27 650 Right column 12 Application Auxiliaries and surfactants, pages 26 to 27, page 650, right column Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is 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.

A coupler which releases a photographically useful residue upon coupling is 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.

[0074]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. (Example) 1) Preparation of base film (A), (B) PET chips and PEN chips were melt extruded, and then stretched 3.4 times in the longitudinal direction and 4 times in the transverse direction to obtain a film having a thickness of 80 μm. In manufacturing the axially stretched polyester film, an infrared heater is installed as an auxiliary heating source on one surface of the longitudinal stretching zone (the surface in contact with the casting drum during casting: hereinafter referred to as CD surface) in the longitudinal stretching zone as shown in FIG. did.

(C) As an example of the polyester blend support, PBB-1 (PEN / PET = 6) is used.
A 0/40 blend) film was made. As the polyester used for the support, pellets of PEN and PET were previously dried under vacuum at 150 ° C. for 4 hours, and then kneaded and extruded at 280 ° C. using a biaxial kneading extruder at the above mixing ratio to prepare pellets. (D) Further, as the polyester having a glass transition temperature of 90 ° C. or higher, the above-mentioned PBC-2 (support composition NDCA / TP
A / EG = 75/25/100 (mol%) copolymer)
It was created. This uses a stainless steel autoclave and uses terephthalic acid (TPA) diethyl as a dicarboxylic acid and 2,6-naphthalenedicarboxylic acid (NDCA).
Ethylene glycol (EG) as dimethyl and diol
Are mixed in the above composition, and antimony trioxide 0.
Using 025 mol (relative to the acid component), polycondensation was carried out by the transesterification method. In addition, the same method as described above for PAr (TPA / bisphenol A = 100/100
(Mol%)) and poly (oxyisophthaloyloxy-
2,6-Dimethylisopropylidene-3,5-dimethyl-1,4-phenylene) (abbreviated as PMeAr) (isophthalic acid / 2,2- [bis (4-hydroxy-3,5-dimethylphenyl)] propane = 100/100 (mol
%) Was polycondensed. These polyesters were stretched in the same manner as above. PEN, PBB-1, PBC-2,
PAr and PMeAr are extruded at a temperature of 300 ° C., longitudinal stretching temperature (CD side) 140 ° C., transverse stretching temperature 130 ° C., heat setting 2
A film was formed at 50 ° C. for 6 seconds. On the other hand, PET has an extrusion temperature of 270.
℃, longitudinal stretching temperature (CD side) 100 ℃, transverse stretching temperature 11
The film was formed at 0 ° C. and heat set at 220 ° C. for 6 seconds. At the time of stretching, the voltage applied to the infrared heater was changed to give a temperature difference between the front and back as shown in Tables 1 and 2, and the supports A-1 to 13 and B were supported.
-1 to 3, C-1, D-1, 2, and 3 were formed into a film. Of these, PMeAr (D-3) was extremely poor in transparency and was not suitable for use as a photographic film.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

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

2) Coating of undercoat layer The supports A1 to 13, B1 to 3, C-1, D-1 and 2 are:
After performing corona discharge treatment on both sides of each of them, 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 processed is 0.3
Treatment of 75 KV · A · min / m ² was performed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. Gelatin 3 g Distilled water 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g

Further, the supports A-1 to 13, B-1 to 3,
Regarding C-1, D-1, and 2, UV irradiation treatment was applied to both surfaces of each, and then an undercoat liquid having the following composition was applied to
After drying at 20 ° C. for 2 minutes, it was wound up. Coating amount is 10cc / m ²
Met. The ultraviolet irradiation treatment was carried out by using the apparatus shown in FIG. 2 described above and performing the ultraviolet irradiation under the above-mentioned stretching and heat setting conditions. Therefore, the irradiation time is 6 seconds, and the irradiation conditions are 3K as described above.
Twelve W high-pressure mercury lamps are arranged at a distance of 0.3 m from the film surface. These samples were A′-1 to 13, B′-1 to 3, C′-1, and D ′, respectively.
-1, 2 and the photosensitive layer coating of the back layer described below is A-1
.About.13, B-1 to 3, C-1, D-1, and 2. Gelatin 1 part by weight Water 1 〃 Acetic acid 1 〃 Methanol 50 〃 Ethylene dichloride 50 〃 p-Chlorophenol 4 〃

3) Coating of back layer Supports A1 to 13, B1 to 3, C-1 and D- after undercoating
A back layer having the following composition was applied on the surface opposite to the side on which the undercoat layers 1 and 2 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 on a stainless steel core having a diameter of 30 cm, with the undercoating surface wound outside. 5) Coating of slipping layer After the above heat treatment, the sliding agent of Table 1 was applied to the back surface by the following formulation (C) so that the dry solid content was 20 mg / m ² , and A-1 to 13 Is 100 ° C. for 2 minutes, B-1 to 3 C-1, D-1, 2 is 55 ° C. 3
Dry for minutes. (Formulation C) Lubricating agent 1 part by weight Xylene 500 parts by weight Comparative Example 1) According to Table 1 as a comparative example, a material which was not subjected to the heat treatment in the above examples was prepared. Comparative Example 2) As a comparative example, a PEN support is used in the above example,
The thing which did not apply a sliding layer was prepared. Comparative Example 3) As a comparative example, one prepared by applying heat treatment after applying the lubricant in the above example was prepared.

Among the mechanical strengths of these supports, the bending elasticity, which is the most important with the thinning of the supports, was measured. The bending elastic modulus was measured by using a method called a ring method. That is, a sample having a width of 35 mm and slits parallel to the length direction was used to form a circular ring having a circumference of 10 cm, which was placed horizontally. The load at the time of deformation of this ring was measured by 12 mm 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 80 μm and TAC is 122 μm
The bending elastic modulus corresponding to is shown. Further, this value did not change even when the heat treatment of the present invention was performed.

6) 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 11 and B-.
1-3, C-1, D-1, and 2 were 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

[0089]

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

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 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

9th 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

12th 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 the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0104]

[Table 5]

In Table 3, (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.

[0106]

[Chemical 10]

[0107]

[Chemical 11]

[0108]

[Chemical 12]

[0109]

[Chemical 13]

[0110]

[Chemical 14]

[0111]

[Chemical 15]

[0112]

[Chemical 16]

[0113]

[Chemical 17]

[0114]

[Chemical 18]

[0115]

[Chemical 19]

[0116]

[Chemical 20]

[0117]

[Chemical 21]

[0118]

[Chemical formula 22]

[0119]

[Chemical formula 23]

[0120]

[Chemical formula 24]

7) Sample Evaluation Photographic film samples A-1 to A-1 thus prepared
Winding evaluation was performed on 11, B-1 to 3, C-1, D-1, and 2. The evaluation was performed according to the following procedure. 7-1) 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. 7-2) Development processing and curl measurement After the film wound under the above conditions is allowed to cool overnight in a room at 25 ° C, 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 Fixing 38 ° C. 2 minutes Water wash 38 ° C. 1 minute Stabilizing bath: 38 ° C. for 1 minute The treatment liquid 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

(7-3) Evaluation of slip characteristics The slip characteristics of the samples prepared by the procedure up to (6) were evaluated by the following method. (1) Measurement of static friction coefficient The sample was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then measured with a HEIDON-10 static friction coefficient measuring machine to measure 5 mm.
The measurement was performed using a φ W stainless steel ball. The smaller the value, the better the slipperiness. (2) Measurement of dynamic friction coefficient The sample was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then, a HEIDON-14 dynamic friction coefficient measuring machine was used to measure 5 mm.
φ stainless steel ball load 100g, friction speed 60cm / min
It was measured at. The smaller the value, the better the slipperiness.

(8) Results The results are shown in Tables 1 and 2. With PEN, PBB-1, PBC-2, and PAr having a glass transition temperature of more than 90 ° C, curl decompression was shown in about 6 hours when a temperature difference was applied during stretching. Rate 33
In the case of g, PBB-1, and PBC-1, it becomes 30 g,
The value is close to 36 g at TAC 122 μm. Therefore, PEN, PBB-1, PBC- which has been treated according to the present invention
2. By using PAr, even if it is wound on a thin spool with a diameter of 8 mm, there is almost no hindrance that would actually cause damage, and
There is an advantage that the support can be thinned to 80 μm.

On the other hand, PE having a glass transition temperature of 90 ° C. or lower
In T, the curl is not reduced even if the heat treatment, the temperature difference during stretching, and any combination thereof are used. Further, with PMeAr having a glass transition point of 200 ° C. or higher, a film having good transparency was not obtained, and it was not suitable for use as a photographic light-sensitive material. Further, when a slipping layer was applied and when the method of the present invention was used, the slipperiness of the back surface was improved, and the problems of repelling during coating of the photosensitive layer and defective adhesion of the photosensitive layer did not occur. Further, these samples had no particular problem of photographic property and could be preferably used as a silver halide photographic light-sensitive material. On the other hand, when the heat treatment was performed after applying the slip layer as in Comparative Examples 3-1 to 3-8, the slip property deteriorated. For 3-1 and 3-2, repelling occurred when the photosensitive layer was applied, and for 3-4 and 3-7, defective adhesion of the photosensitive layer occurred. Samples A'-1 to 1 in which an undercoat layer was applied after UV treatment
Similar results were obtained for 3, B'-1 to 3, C'-1, D'-1, and 2.

(Example 2) 1) Preparation of support film A PEN support was coated up to the back layer in the same manner as in Example 1 except that the coating solution (B) for coating at the time of coating the back layer was not applied. After installation, heat treatment was performed under the conditions shown in Table 4 to prepare samples E-1 to 9 and E'-1 to 9.
All the heat treatments were carried out on a stainless steel core having a diameter of 30 cm, with the undercoat surface being wound outside. After the heat treatment, the coating solution of the following formulation (D) containing the slip agent shown in Table 4 had a dry film thickness of 0.
It was applied so as to have a thickness of 1 μm and dried at 100 ° C. for 2 minutes. (Slip coating liquid for coating (D)) 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 Sliding agent 0.5 parts by weight Comparative Example 4) As a comparative example, Samples 4-1 to 4-9 which were heat-treated after coating the sliding layer in the above examples were prepared. With respect to the above-mentioned support samples, the flexural characteristic rate was measured by the ring method in the same manner as in Example 1. Further, a photosensitive layer was applied according to Example 1 to prepare the samples shown in Table 4. The conditions and results are shown in Tables 4 and 5 below.

[0127]

[Table 6]

[0128]

[Table 7]

(2) Evaluation of Samples Samples E-1 to 9 and 4-1 created in this way
14 was wound in the same manner as in Example 1 and the slip characteristics were evaluated.

(3) Results The results are shown in Tables 4 and 5. Similar to Example 1, PEN having a glass transition point of higher than 90 ° C. exhibits a curl reducing effect,
There was almost no curse that could actually cause harm. Further, when a sliding layer is provided, E-1 to 9 produced by the method of the present invention
Then, the slipperiness of the back surface was improved, and the problems of repelling during coating of the photosensitive layer and defective adhesion of the photosensitive layer did not occur.
Further, these samples had no particular problem of photographic property and could be preferably used as a silver halide photographic light-sensitive material. On the other hand, when the heat treatment was performed after applying the slip layer as in Comparative Examples 4-1 to 4-9, the slip property deteriorated. Regarding 4-1 and 4-2,
The repellency at the time of coating the photosensitive layer is 4-5 and 4-6,
Poor adhesion of the photosensitive layer occurred. Similar results were also obtained for Samples E'-1 to 9 in which the undercoat layer was applied after the UV treatment.

[0131]

By carrying out the present invention, it is possible to provide a silver halide photographic light-sensitive material which is hard to curl up, has strong mechanical properties and has good slidability, and a method for producing the same.

[Brief description of drawings]

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

FIG. 2 shows a side view of the stretching device of the present invention.

[Explanation of symbols]

 1. Film 2.3. Longitudinal stretching roller 4. Cooling roller 5. Infrared heater 6. Preheated transverse stretching zone 7. Heat setting and irradiation zone 8. Cooling zone 9. High-pressure mercury lamp 10. Reflector 11. Exhaust 12. Hot air supply 13. Cold air supply 14. Fastening frame 15. Winding

Claims (7)

[Claims] 1. A polyester film support having at least one photosensitive silver halide emulsion layer on at least one surface thereof, and the glass transition temperature of the polyester film support is 90 ° C. or higher and 200 ° C. or lower, and In the silver halide photographic light-sensitive material, the polyester film support is heat-treated at a temperature of 50 ° C. or higher and a glass transition point of the polyester film or lower in the period from the film formation to the coating of the photosensitive layer. A silver halide photographic light-sensitive material characterized in that after a heat treatment at a temperature not higher than the transition point, a sliding layer is coated on the surface of the support opposite to the surface on which the silver halide emulsion layer is coated. 2. The sliding agent contained in the sliding layer is at least one kind of sliding agent selected from organopolysiloxane, higher fatty acid and its derivative, higher alcohol and its derivative, and paraffin. A silver halide photographic light-sensitive material according to claim 1, and a method for producing the same. 3. The halogen according to claim 1, wherein the slip agent contained in the slip layer is at least one kind of slip agent selected from the following general formulas (1) to (4). Silver halide photographic light-sensitive material and its manufacturing method. [Chemical 1] In the formula, R ₁₁ represents a linear aliphatic hydrocarbon group having 11 or more carbon atoms, and R ₁₂ represents a linear aliphatic hydrocarbon group having 25 or more carbon atoms. R ₁₃ and R ₁₄ each represent an aliphatic hydrocarbon group having 12 or more carbon atoms, and either R ₁₃ or R ₁₄ represents a branched aliphatic hydrocarbon group. Further, the total carbon number of R ₁₃ and R ₁₄ is 32 or more. R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ each represent a linear or branched aliphatic hydrocarbon group having 12 or more carbon atoms, and X represents a divalent linking group. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester film support is composed of a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components, and a method for producing the same. 5. The polyester film has a thickness of 50 μm.
2. The thickness is not less than m and not more than 300 μm.
To 4, and a method for producing the same. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester film support is polyethylene-2,6-naphthalene dicarboxylate, and a method for producing the same. 7. The method for producing the silver halide photographic light-sensitive material according to claim 1, 2.