JPH06123937A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a photographic sensitive material excellent in dynamic property, small in curling property and excellent in flatness and to provide a producing method. CONSTITUTION:In a silver halide photographic sensitive material having at least one layer of a photosensitive silver halide emulsion layer on at least one side of a polyester film supporting body, the supporting body is heat-treated at >=50 deg.C to a temp. below the glass transition point of the supporting body in a period after film forming to photosensitive layer coating and the creak value between front and rear faces of the supporting body at the time of winding before heat treating is <=400g to >=10g.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and particularly to a surface of 10 ° C. or more and 100 °
A silver halide photographic light-sensitive material having less tendency to curl and a method for producing the same, which has as a support a polyester heat-treated at a temperature not lower than 50 ° C. and not lower than a glass transition temperature of the support of not lower than 50 ° C. Is.

[0002]

2. Description of the Related Art A support for a photographic light-sensitive material is generally a fiber type polymer represented by triacetyl cellulose (hereinafter referred to as "TAC") and a polyester represented by polyethylene terephthalate (hereinafter referred to as "PET"). Polymers of the system have been used. In general, photographic light-sensitive materials are in sheet form such as X-ray film, plate-making film and cut film, and typical roll films are 35 m / m width or less in a cartridge. It is a color or black-and-white negative film that is stored and is used in a general camera for shooting. TAC is mainly used as a support for a roll film, which is characterized by high optical transparency. Further, it has excellent properties in decurling after development processing. On the other hand, the PET film has excellent productivity, mechanical strength, and dimensional stability, but in a roll form widely used as a photographic light-sensitive material, curling curl remains strongly, and thus it is easy to handle after development processing. However, 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. At that time, a support for a photographic light-sensitive material is required to have properties such as strength, dimensional stability, and thinning. Further, with the downsizing of the photographing device, there is an increasing demand for downsizing of the cartridge. In order to miniaturize the Patrone, there are two problems. The first problem is a decrease in mechanical strength as the film becomes thinner. The second problem is the strong curl that occurs during storage over time as the spool becomes smaller. On the other hand, if the smoothness of the inner surface and the outer surface of the roll when the film is wound during production of the film support is high, or if the coefficient of dynamic friction between the inner surface and the outer surface is high, creaking occurs during winding, resulting in fine scratches. Occur. In addition, when heat treatment is performed, stretching or contraction of the film is non-uniform due to poor slidability, and wrinkles occur in the film.
Since the flatness becomes poor, and the films stick together (blocking) while containing the air layer between each winding layer, a blocking mark is generated by heat treatment, and the flatness becomes poor. Has become.

Several attempts have hitherto been made as methods for reducing the curl of a polyester film. For example, a method described in JP-A-51-16358, that is, a method of performing heat treatment at a temperature lower than the glass transition temperature by 30 ° C to 5 ° C is known.

On the other hand, a method as disclosed in Japanese Patent Application Laid-Open No. 1-131550, that is, a structure is provided in the base so that a curl is formed in a direction opposite to the winding direction as a product,
There is a method of canceling out the curl that occurs during product storage.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photographic light-sensitive material having excellent mechanical properties, less curl, and good flatness, and a method for producing the same. is there.

[0007]

The present invention provides a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a polyester film support, the support being provided after film formation. Before coating the photosensitive layer, it is heat-treated in a roll form at a temperature of 50 ° C. or higher and the glass transition temperature of the support or lower, and the squeaky value between the front and back surfaces of the support before winding is 10 g. It was achieved by a silver halide photographic light-sensitive material characterized by being 400 g or less.

The temperature exposed to general users is usually 50 to 60 ° C., and in rare cases, the temperature in the vehicle in summer may exceed 80 ° C. Therefore, it is necessary that the polyester support of the present invention has a glass transition temperature of at least 60 ° C or higher, more preferably 90 ° C or higher and 200 ° C or lower.

Although there are various polyesters as described above, a polyester having naphthalenedicarboxylic acid and ethylene glycol as the main raw materials has a high performance by balancing both the difficulty of rolling and the mechanical strength. Especially, it was polyethylene-2,6-naphthalene dicarboxylate (PEN). These supports need to have a thickness of 50 μm or more and 300 μm or less.

The heat treatment must be performed 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. 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, more preferably 30 ° C. or lower.
It is below the glass transition temperature above the temperature below ℃. On the other hand, when the heat treatment is performed under this temperature condition, the effect is recognized after 0.1 hour. On the other hand, at 1500 hours or more, the effect is almost saturated. Therefore, it is necessary to perform heat treatment for 0.1 hour or more and 1500 hours or less.

The present invention will be described in more detail below. However, the present invention is not limited to these. First, the polyester used in the present invention will be described. The polyester 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,
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, tetrachloroanhydride Phthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid,

[0012]

[Chemical 1]

[0013]

[Chemical 2]

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

[0015]

[Chemical 3]

[0016]

[Chemical 4]

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

[0018]

[Chemical 5]

Among the polyesters composed of these diols and dicarboxylic acids, more preferred is P
ET polyethylene-2,6-dinaphthalate (PE
N), polyarylate (PAr), homopolymers such as polycyclohexanedimethanol terephthalate (PCT), and dicarboxylic acid 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), Orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), paraphenylenedicarboxylic acid (PPDC), diols such as ethylene glycol (EG), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA), Biphenol (BP) Also, as the hydroxycarboxylic acid, there can be mentioned those obtained by copolymerizing parahydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA).
Among these, those having a glass transition temperature (Tg) of 90 ° C. or higher and 200 ° C. or lower are preferable. Specifically, naphthalene dicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 and 1.0: 0, 0.5: 0.5 to 0.8: 0.2 is more preferable), a copolymer of terephthalic acid, ethylene glycol and bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is 0.6: 0.4 to 0: 1. 0
Is more preferable, and 0.5: 0.5 to 0: 0.9 is more preferable. ), Isophthalic acid, paraphenylenedicarboxylic acid, and a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0.1 to 1 when terephthalic acid is 1).
0.0, 0.1 to 20.0, and more preferably 0.2 to 5.0 and 0.2 to 10.0), naphthalenedicarboxylic acid, and a copolymer of neopentyl glycol and ethylene glycol (neo). The molar ratio of pentyl 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) terephthalic acid, a copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2,
More preferably, it is 0.1: 0.9 to 0.7: 0.3. ), Para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid, ethylene glycol is 1: 0 to 0.1:
0.9 is preferable, and 0.9: 0.1 is more preferable.
0.2: 0.8) and other copolymers and PEN and PET
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable, and 0.
5: 0.5 to 0.8: 0.2 is more preferable), PET
And PAr (composition ratio of 0.6: 0.4 to 0: 1.0 is preferable, and 0.5: 0.5 to 0: 0.9 is more preferable).

PEN is the most balanced of these polyesters, has a mechanical strength, especially a high elastic modulus, and has a 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.) among these polymers, but has the disadvantage 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 known methods for producing polyesters. If necessary, a heat resistance stabilizer may be added. For these polyester synthesis methods, for example,
Polymer Experimental Science Vol. 5 "Polycondensation and polyaddition"
980) 103-136, "Synthetic Polymer V"
(Asakura Shoten, 1971) 187 to 286 can be referred to. The preferred average molecular weight range for these polyesters is about 5,000 to 10.
It is 10,000.

Polymer blends of the polymers thus obtained are disclosed in JP-A-49-5482 and JP-A-64-5482.
4325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779.
-82, 294, 807-14, it can be easily formed.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Example of polyester 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 a molar ratio.) PBC-12 , 6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. PBC-2 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. PBC-3 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. PBC-4 TPA / EG / BPA (100/50 50) Tg = 105 ° C. PBC-5 TPA / EG / BPA (100/25/75) Tg = 135 ° C. PBC-6 TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. PBC- 7 IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C. PBC-9 TPA / EG / BP (100 / 20/20) 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 = 1 2 ° C. PBB-4 PAr / PCT (50/50) Tg = 118 ° C. PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 All of the polyesters having a temperature of ℃ or higher have a flexural modulus higher than that of TAC, and it is possible to realize the original thinning of the film. However, PEN had the strongest bending elasticity among these, and when it was used, TAC was 1
It is possible to reduce the required film thickness of 22 μm to 80 μm.

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

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 1.5.
It is 0 to 1.55, which is smaller than this value. Therefore, when light is incident from the film edge, it is easily reflected at the interface between the base and the emulsion layer, causing a 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. In the present invention, the preferred method for preventing light piping is a method by adding a dye that does not significantly increase the film haze. The dye to be used is preferably gray dyeing in view of general properties of the light-sensitive material, and the dye is preferably one having excellent heat resistance in the film forming temperature range of the polyester film and excellent compatibility with polyester. 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. The staining density is
It is necessary that the color density in the visible light range is measured with a color densitometer manufactured by Macbeth Co., Ltd. and is at least 0.01 or more. More preferably, it is 0.03 or more.

FIG. 1 shows a side view of the longitudinal stretching zone of a polyester film according to the 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. The film forming step is not particularly limited, but as a preferred example of the present invention, sequential biaxial stretching in which the film is stretched at a specific ratio in the longitudinal direction after casting and further stretched in the lateral direction by a tenter is adopted.

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

Among the surface treatments of (1), the corona discharge treatment is, for example, Japanese Patent Publication Nos. 48-5043 and 47-519.
No. 05, JP-A-47-28067 and JP-A-49-8376.
No. 7, No. 51-41770, No. 51-131576 and the like. The discharge frequency is 50 Hz to 5000 kHz, preferably 5 kHz to several hundreds of kHz. If the discharge frequency is too low,
It is not preferable because stable discharge cannot be obtained and pinholes are formed on the object to be treated. 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 treatment strength of the object to be treated, in order to improve the wettability of plastic films such as ordinary polyester and polyolefin, 0.00
1 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 is suitable.

The glow discharge treatment, which is a surface treatment, is carried out, for example, in Japanese Patent Publication Nos. 35-7578 and 36-10336.
45-22004, 45-22005, 45
-24040, 46-43480, U.S. Pat.
057,792, 3,057,795, 3,1
79,482, 3,288,638, 3,30
9,299, 3,424,735, 3,46
2,335, 3,475,307, 3,76
1,299, British Patent 997,093, JP-A-53
No. 129262 or the like can be used. The glow discharge treatment condition is generally such that the pressure is 0.005 to 20 Torr, preferably 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect will decrease, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is also dangerous.
There is also a risk of destroying the object to be processed. 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 to 50 within the above pressure range.
A stable steady glow discharge occurs between 00V. A particularly suitable voltage range for improving the adhesion is 2000-40
It is 00V.

The discharge frequency is from direct current to several thousand MHz, preferably 50 Hz, as seen in the prior art.
20MHz is suitable. Regarding the discharge treatment strength, 0.01 KV · A · min /
m ^{2 to 5} KV · A · minute / m ² , preferably 0.15 KV · A · minute / m ^{2 to 1} KV · A · minute / m ² . Further, UV treatment which is particularly preferable as a pretreatment for an organic solvent-based undercoat is carried out by any conventionally known method, for example, Japanese Patent Application No. 39-145.
No. 34, No. 39-16094, Japanese Patent Publication No. 45-3828
No. etc. 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 it is possible to improve the efficiency of irradiation of ultraviolet rays as compared with the case of performing irradiation after film formation. 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 the irradiation treatment is carried out at a high temperature of ° C, it is advantageous in that the intended purpose can be achieved with an irradiation time of 1/2 to 2/3 as compared with the irradiation after heat setting. Although there is an advantage in that the length of the mercury lamp can be short when UV irradiation is performed before or during the stretching, the processing efficiency is reduced because the temperature is limited to a relatively low temperature. It is inferior to the case of irradiation during heat setting.

The film-forming undercoating process of the photographic film support has two steps.
The film support melted at a temperature of 90 ° C. to 300 ° C. and extruded onto a cooling drum is then subjected to a heat roll heated to a temperature of 85 ° C. to 90 ° C. for 2.5 hours in a longitudinal direction while passing through the heated roll.
~ 3.3 times stretched. 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. In the width direction at a temperature range of 95 ° C to 110 ° C from 2.5 to
It is stretched 3.3 times and then heat set at a temperature of 210 ° 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 3 KW high-pressure mercury lamps made of quartz tubes and having an effective arc length of about 1 m are installed in the heat fixing zone at intervals of 1 m. (Fig. 2
9) Also, the mercury lamps are arranged in parallel at a distance of 0.3 m from the film surface, and each lamp is equipped with a chrome-plated reflector (10 in Fig. 2) to improve the irradiation efficiency. It has become. 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)
Represents exhausted air, (12) represents hot air, (13) represents cold air, (14) represents a frame for staying, and (15) represents 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 the organic solvent, additives for the purpose of reinforcing the undercoat layer, improving the adhesiveness with the support or the emulsion layer, antistatic, or 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 that are particularly effective in the present invention have a wavelength of 3200 to 2
It is an ultraviolet ray between 200Å.

Next, the undercoating method (2) is selected from, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. in the first undercoating layer in the multi-layer method. The properties of many polymers such as copolymers using monomers as starting materials, polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and mainly gelatin in the second undercoat layer have been investigated. 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. Of these, gelatin is the most preferable. As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, Examples include trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred.

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

The hydrophilic binder used in the present invention has --OH, --COOH, O = (O
C) ₂ =, -SO ₃ M (M is H or an alkali metal) -N
H ₂ , cyclic amide-CONR ₁ R ₂ (R ₁ and R ₂ are H or an alkyl group having C = 4 or less), or a heterocyclic group containing nitrogen, etc., alone or in combination of two or more, and is compatible with an organic solvent. Synthetic polymer compound that swells or dissolves in water when dissolved: For example, cellulose acetate phthalate, cellulose acetate maleate, vinyl copolymer containing maleic anhydride, for example, vinyl acetate and maleic anhydride (1: 1) copolymer (See German Patent No. 1040898 if necessary), mixed acetal compounds containing SO ₃ M groups of polyvinyl alcohol (see British Patent No. 984509), mixed acetals containing —COOM groups of polyvinyl alcohol, or divalent acid moieties. Many hydrophilic resins can be mentioned, such as esterified products and a mixture of polyvinylpyrrolidone and polyacrylic acid. Instead of the hydrophilic binder solution described above, an undercoat liquid composed of a gelatin dispersion liquid may be used.

Examples of the solvent or swelling agent for the polyester used in the present invention include ketones or aldehydes containing an aromatic or partially saturated aromatic group and aldehydes having a heterocyclic group containing nitrogen (UK Patent No. 772600), a carboxylic acid represented by the general formula R-COOH or R-X-COOH, or an anhydride thereof, an ester, an amide, or a nitrile obtained from the acid, wherein R is aromatic or nitrogen in the ring. An aromatic heterocyclic compound containing X, X is —CH ₂ or —OC
H ₂ (see British Patent No. 777,157), aliphatic monohydric alcohols or amines containing an aromatic group (see British Patent No. 785789), alcohols, ketones, carboxylic acids and substituents thereof or esters thereof. (British Patent No. 797425), -NO ₂ to the aromatic nucleus, benzyl alcohol (US Patent No. 2,830,030) was substituted for -Cl, chloral hydrate (German Patent No. 1020457), pyrrole (German Patent No. 1,092,652) Etc., and specific examples of the solvent described above include benzoic acid, salicylic acid, salicylic acid ester, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-nitropropanol, benzyl alcohol, benzaldehyde, aceto. Nylacetone, acetophenone, Ntsuamido, benzonitrile,
Examples thereof include benzylamine and methyl nicotinate. In addition to these, as the solvent or swelling agent of the known polyester, there are 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 the swelling agent as exemplified above in the undercoating liquid component. When it is 25% or more, the flatness of the finished film is often significantly impaired, and when it is 1% or less, the desired effect is scarce. Of course,
Two or more polyester solvents or swelling agents may be mixed and used at the same time. In this case, the addition amount is such that 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 a well-known coating method, for example, tip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by the extrusion coating method using the hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by the method described in “Coating Engineering”, page 253 (1973, published by Asakura Shoten).

If desired, a back layer may be provided on the surface (back surface) of the polyester support of the present invention opposite to the side on which the photosensitive layer is provided. The binder for the back layer may be a hydrophobic polymer or a hydrophilic polymer used in the underlayer. 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 examples of the anionic polymer electrolyte include polymers containing a carboxylic acid, a carboxylic acid salt and a sulfonic acid salt, for example, JP-A-48-22017. , Tokkyo Sho 46-24
159, JP-A-51-30725 and JP-A-51-1.
29216 and Japanese Patent Application Laid-Open No. 55-95942. Examples of the cationic polymer include JP-A-49-121523 and JP-A-48-911.
65 and Japanese Patent Publication No. 49-24582. In addition, ionic surfactants are also anionic and cationic. For example, JP-A-49-85826.
No. 49,33630, US Pat. No. 2,992,10
8, US 3,206,312, JP-A-48-87826.
Issue, Japanese Examined Patent Publication No. 49-11567, Japanese Examined Patent Publication No. 49-1156
No. 8, JP-A-55-70837 and the like can be mentioned.

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

Next, the means for imparting slipperiness to the polyester film, which is an important requirement of the present invention, will be described in detail. The imparting of slipperiness of the present invention reduces the squeaking of the front and back surfaces of the base when wound, thereby reducing the heat shrinkage stress generated during the heat treatment, and thereby preventing the decrease in flatness and scratches. To implement. For this purpose, the squeaky value needs to be 400 g or less. On the other hand, 10g
In the following, the bases are too slippery to be able to be wound neatly. Therefore, a squeaky value of 10 g or more and 400 g or less is required. To give the polyester film slipperiness,
It is applied to the outermost layer on one side or both sides of the roll before the step of heat treatment for improving the winding tendency. The means for imparting slipperiness to the polyester film is not particularly limited, but a method of increasing the surface roughness and a method of imparting slippage to the surface are common. As a method for increasing the surface roughness, one is to knead a matting agent into a polyester film, and the second is to apply a surface matting layer to at least one side of the film. The surface roughness of the polyester film desired in the present invention is 0.01 μm to 5 μm as an average surface roughness.
m is desirable. When the surface roughness is 0.01 μm or less, squeaking and blocking resistance cannot be obtained, and when the surface roughness is 5 μm or more, the matting agent may appear when used as a photographic light-sensitive material, which is not suitable as a photographic film. As the matting agent to be used, inert inorganic particles are preferable because when the polyester film is kneaded, the film is formed at a high temperature. Specifically, SiO ₂ , Ti
Examples thereof include O ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. In addition to the above-mentioned method of adding slipperiness by means of an external particle system in which inert particles are added to the polyester synthesis reaction system, a method of imparting slipperiness by means of an internal particle system for precipitating a catalyst or the like added during the polyester polymerization reaction can also be adopted. Is. In the above means for imparting slipperiness, SiO ₂ having a refractive index relatively close to that of the polyester film as the external particle system,
Alternatively, it is desirable to select an internal particle system that can make the precipitated particle system relatively small.

The particle size of the matting agent is not particularly limited as long as the above surface roughness is obtained, but is preferably 0.01.
μm to 10 μm, more preferably 0.05 to 5 μm. The addition amount of the matting agent is limited from the viewpoint of imparting surface roughness and transparency of the film, and is 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, based on the polyester. Is.

When the surface roughness is imparted to the polyester film by kneading, it is desirable that the above-mentioned heat treatment step is carried out before coating another layer on the film upper layer.
Further, regarding the coating of the surface matting layer, it is desirable to coat the surface matting layer so that it is the outermost layer of at least one of the undercoating surface and the back surface or the both surfaces at the time of winding before the heat treatment step. As the matting agent, an inorganic compound or a polymer compound having a glass transition temperature of 50 ° C. or higher is desirable.
The Tg of the polymer compound matting agent is more preferably T
Two or more kinds of these matting agents having a g of 60 ° C. or more, and more preferably 65 ° C. or more may be mixed and used. Examples of the inorganic compound of the matting agent of the present invention include fine powders of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide. Examples thereof include silicon dioxide such as the obtained synthetic silica, and titanium dioxide (rutile type or anatase type) produced by titanium slag and sulfuric acid. It can also be obtained by crushing from an inorganic material having a relatively large particle size, for example, 20 μm or more, and then classifying (vibrating filtration, air classification, etc.). Further preferable examples of the matting agent of an inorganic compound include fine particles having conductivity. Specifically, ZnO,
TiO ₃ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO
It is fine particles of at least one crystalline metal oxide selected from ₂ , MgO, BaO and MoO ₃ or a composite oxide thereof. By using this as a matting agent,
It is possible to prevent dust from accumulating due to static electricity that occurs when it is wound up on a roll. In the present invention, heat treatment is performed after winding, but at this time, dust is likely to be entrapped due to static electricity and unevenness due to this is likely to occur. However, by using the film coated with the conductive fine particles as described above, these failures can be suppressed. Also, in the case of polymer compounds, polytetrafluoroethylene, cellulose acetate,
There are polystyrene, polymethylmethacrylate, polypropylmethacrylate, polymethylacrylate, polyethylene carbonate, starch and the like, and also pulverized and classified products thereof. Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound spherically formed by a spray drying method or a dispersion method, or an inorganic compound can be used. In addition, one of the monomer compounds described below
The polymer compound which is a polymer of one kind or two or more kinds may be formed into particles by various means.

For example, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes and olefins are preferably used. Further, the present invention includes JP-A Nos. 62-14647, 62-17744, and 62.
Particles having a fluorine atom or a silicon atom as described in No. 17743 may be used. Among these, the particle composition preferably used is polystyrene, polymethyl (meth) acrylate, polyethylacrylate, poly (methylmethacrylate / methacrylic acid = 95/5 (molar ratio), poly (styrene / styrenesulfonic acid = 95/5 ( Molar ratio), polyacrylonitrile,
Examples thereof include poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50/40/10) and silica. Further, the particles of the present invention are disclosed in JP-A-64-77.
It is also possible to use the particles having reactive (in particular gelatin) groups described in 052 and EP 307855. Further, a large amount of groups that can be dissolved in alkaline or acid can be contained.

The particle size of the matting agent used in the present invention is preferably 0.005 μm to 10 μm, more preferably 0.01 μm to 5 μm. The amount of the matting agent used in the present invention is 5 to 500 mg.
/ M ² is preferred, more preferably 10 to 200 mg / m ²
Is. The matting agent is preferably used in a large amount for blocking resistance, but is limited from the viewpoint of increasing haze and deteriorating photographic properties. In coating the matting agent, it is preferable to use it together with a binder capable of forming a film. Examples of such polymers include known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins,
And hydrophilic binders such as mixtures thereof, gelatin and the like can be used.

As the above-mentioned thermoplastic resin, cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyacetyl cellulose phthalate, cellulose linear alkyl ester, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate. Cellulose derivatives such as resin, 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.

Polar groups (epoxy group, CO ₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M,
OSO 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 binder is described in Research Disclosure No. 17643, page 26, and No. 18716, page 651. Water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. 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, acrylate ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers and the like. Of these, gelatin is the most 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 hardeners include formaldehyde,
Aldehyde compounds such as glutaraldehyde, ketone compounds such as diacetyl, cyclopentanedione,
Bis (2-chloroethylurea), 2-hydroxy-4,
6-dichloro-1,3,5-triazine, other compounds having reactive halogen, divinyl sulfone, 5
-Acetyl-1,3-diacryloylhexahydro-
1,3,5-triazine, compounds having reactive olefins, N-hydroxymethylphthalimide, N-methylol compounds, isocyanates, aziridine compounds, acid derivatives, epoxy compounds, halogens such as mucochloric acid Carboxaldehydes can be mentioned. Alternatively, as the inorganic compound hardening agent, chromium alum, zirconium sulfate and the like can be mentioned. Further, a carboxyl group-activating type hardener and the like can also be used.

Another means for imparting slipperiness to the polyester film is to coat a lubricant on the outermost layer. The slipping agent contained in the slipping layer in the present invention is a surface active agent such as paraffin, organopolysiloxane, higher fatty acid and its derivative, higher alcohol and its derivative, which are generally used as a material for giving slipperiness. Etc. can be used. The higher fatty acid and its derivative, the higher alcohol and its derivative include higher fatty acid, metal salt of higher fatty acid, higher fatty acid ester, higher fatty acid amide, polyhydric alcohol ester of higher fatty acid, etc., higher aliphatic alcohol, higher aliphatic Ethylene oxide adduct of alcohol, monoalkyl phosphite, dialkyl phosphite, trialkyl phosphite, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, amide compound thereof Alternatively, a salt thereof or the like can be used. Further, JP-B-53-292 and JP-B-59-46, which are known as a slip agent used in a photographic light-sensitive material system.
No. 49, Japanese Patent Publication No. 55-49294, organopolysiloxane derivatives, and the following general formula (1)
It is more preferable to use the higher aliphatic alkyl compound derivative as shown in (4) to (4).

[0050]

[Chemical 6]

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. By using such a slipping agent, it is possible to obtain a silver halide photographic light-sensitive material which has excellent scratching strength, does not cause repellency on the undercoat surface, and does not deteriorate in slipperiness due to development processing of the photographic light-sensitive material. The amount of the lubricant used in the present invention is not particularly limited, but its content is preferably 0.0005 to 2 g / m ² , more preferably 0.001 to 1 g / m ² , and particularly preferably 0.002 to 0. It is 0.5 g / m ² .

The surface layer containing the above-mentioned slipping agent is prepared by dissolving 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.), hydrocarbons (hexane, cyclohexane, etc.) halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene,
Toluene, xylene, benzyl alcohol, benzoic acid,
Anisole, etc., amide type (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, etc. are preferable. The above slip agent may be applied only with a slip agent,
You may use together with the binder used when using the above-mentioned matting agent. At this time, the above-mentioned matting agent may or may not be contained in the sliding layer, but it is preferable to contain the matting agent.

Next, the winding and heat treatment steps in the present invention will be described. First, the core in the winding step will be described. The core is 500000 kg / cm ² in a temperature range of 50 ° C. or higher and the glass transition temperature of the polyester or lower.
It is desirable to have the above elastic modulus and have a temperature coefficient of the elastic modulus of 30 or less. The elastic modulus is more preferably 5500
It is 00 kg. The temperature coefficient of elastic modulus is preferably 30 or less, more preferably 25 or less. It is essential that the cross section of the winding core having these characteristics of the present invention is a perfect circle. The material for these winding cores is not particularly limited as long as it has the elastic modulus of the present invention, but metal, ceramic or ceramic coated metal is preferable. Here, preferable examples of the metal include aluminum, stainless steel (indicating an alloy of iron, chromium and nickel), brass (an alloy of copper and nickel), copper, iron and duralumin (an alloy containing copper, magnesium, manganese and silicon). Of these, aluminum, stainless steel, and iron are more preferable. The ceramic material is not particularly limited, but 3Al ₂ O ₃ -2S is preferable.
_{IO 2, BaTiO 3, SrTiO 3} , Y 2 O 3 -Th
O ₂ , ZrTiO ₃ , ZrO ₂ , Si ₃ N, SiCMg
_{O · SiO 2, MgCv 2 O} 2 -T O 2, can be mentioned, particularly preferred are, 3Al ₂ O ₃ -2SiO
₂ , BaTiO ₃ , SiTiO ₃ , and ZrO ₂ .
Further, the winding core of the present invention may be a mixture or laminate of two or more kinds of materials. For example, if the surface of aluminum is A
It may be coated with 1 ₂ O ₃ or CrO ₂ . Alternatively, the surface of the stainless steel material may be coated with CrO ₂ or, in some cases, a very thin surface coating with a fluororesin.

The core of the present invention has a diameter (outer diameter) of 5 cm or more, more preferably 7 cm to 2 m, still more preferably 10 cm to 1.5 m, and particularly preferably 15 cm.
cm to 1 m. When the polyester of the present invention is wound on the winding core of the present invention, the front and back are not particularly limited, but it is preferable to wind the polyester with the surface opposite to the curling direction facing inward. Next, the heat treatment method for the polyester of the present invention will be described. The polyester of the present invention has a temperature of 50 ° C.
As described above, the polyester is wound around the core of the present invention at a temperature not higher than Tg, but as a method of applying the temperature at that time, immediately after film formation or undercoating, without cooling, at a high temperature (50 ° C. or higher, the polyester (Tg or less) is preferable. Furthermore, the winding core is preferably heated to a temperature at which it is preheated. At this time, the center of the winding core is made hollow so as to reach a predetermined temperature in a short time and heated with a heat medium (for example, hot water, steam, oil (for example, silicone foil, edible oil, mineral oil, etc.)). Can be achieved. In addition, this method makes it easy to cool the core after heating, which is advantageous in manufacturing. At this time, the thickness of the material of the present invention on the outer side of the winding core is not particularly limited as long as the polyester of the present invention can be used without deformation,
It is preferably 2 mm or more, more preferably 5 mm or more,
Particularly preferably, it is 1 cm or more. In the core of the present invention, the polyester to be treated at a high temperature is involved,
There is no particular limitation during the coating or the coating length. The width is preferably 0.1 to 10 m, more preferably 0.5 to 5 m, still more preferably 1 to 5 m.
The coating length is preferably 50 to 10,000 m,
More preferably 500 to 8000 m, even more preferably 1
000 to 5000 m.

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 layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support, and a silver halide emulsion. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting 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 a color sensitivity to any of blue light, green light, and red light. 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 a coupler, a DIR compound, etc. as described in the specification, and may contain a color mixing inhibitor as is commonly used. . A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,4.
70 or British Patent No. 923,045, JP-A-5
7-112751, 62-200350, 62
-206541, 62-206543, 56-
25738, 62-63936, 59-202.
No. 464, Japanese Patent Publication Nos. 55-34932, 49-154
No. 95. The silver halide grains are
Those with regular crystals such as cubes, octahedra and tetradecahedrons, those with irregular crystal shapes such as spheres and plates, those with crystal defects such as twin planes, or those It may be a composite type.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types",
And the method described in the same No. 18716 (November 1979) and the like. Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 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, Photographic Scienc.
e and Engineering), Volume 14, pp. 248-257 (1
970); U.S. Pat. Nos. 4,434,226, 4,
No. 414, 310, No. 4,433, 048, No. 4, 4
It can be easily prepared by the method described in 39,520 and British Patent 2,112,157.
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 compounds 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 to right column 8 Dye image stabilizer Page 25 25 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, 61-72238, 6).
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
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 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 the polymerized dye-forming couplers are U.S. Pat.
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, 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. 2, 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.

Of high boiling point solvents used in the oil-in-water dispersion method
Examples are described in US Pat. No. 2,322,027, etc.
There is. 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, esters of phosphoric acid or phosphonic acid,
Benzoic acid esters, amides, alcohols or phenols
Knols, aliphatic carboxylic acid esters, aniline derivatives
Body, hydrocarbons and the like. Also as an auxiliary solvent
Has a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 16
Organic solvents below 0 ℃ can be used, and vinegar is a typical example.
Ethyl acid, butyl acetate, ethyl propionate, methyl ether
Tillketone, cyclohexanone, 2-ethoxyethyl
Examples include cetate and dimethylformamide. La
Latex for tex dispersion process, effect and impregnation
A specific example is U.S. Pat. No. 4,199,363, unique to Nishi
License application (OLS) Nos. 2,541,274 and
No. 2,541,230. Of the present invention
The light-sensitive material is a film of the all-hydrophilic colloid layer on the side having the emulsion layer.
The total thickness is 28 μm or less, and the film swelling speed T¹/
₂Is preferably 30 seconds or less. The film thickness is 25 ° C and relative humidity is 5
Means the film thickness measured under 5% humidity control (2 days), and the film swelling speed
Degree T¹/ ₂According to techniques known in the art
Can be measured. For example, A Green (A. Gree
n) Photographic Science and
Engineering (Photogr. Sci. Eng.), Volume 19, 2
No., pp. 124-129.
Can be measured by using¹/₂Is the color appearance
Maximum expansion reached when treated with image liquid at 30 ° C for 3 minutes and 15 seconds
90% of the wet film thickness is taken as the saturated film thickness, and this T¹/₂Reaching the film thickness of
It is defined as the time to reach. Membrane swelling speed T¹/₂Is the
There is a hardener added to gelatin as an inder
Or can be adjusted by changing the aging condition after coating.
You can The swelling rate is preferably 150-400%.
Yes. The swelling rate is the maximum swollen film thickness under the conditions described above.
Calculated according to the formula: (maximum swollen film thickness-film thickness) / film thickness
it can.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, and N.
Development can be carried out by a usual method described in the left column to the right column of 615 of o. 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.

[0064]

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

First, a description will be given of winding curl measurement methods used hereinafter, surface roughness and slipperiness measurement methods, terms relating thereto, and the like. (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
The arithmetic average temperature of the temperature at which the temperature starts to deviate from the baseline and the temperature at which the temperature returns to a new baseline when mg is heated at 20 ° C./min in a nitrogen stream is defined as Tg. (8) Squeaky value 180 mm x TD direction (transverse direction) of the film sample
Cut out a rectangle of 50 mm in the MD direction (deposition direction), and cut this on a smooth plate, the surface opposite to the surface on which the photosensitive layer is to be coated (BC surface)
Stick it on (Sample A). This is attached horizontally to the moving stage of the tensile tester (Fig. 4).
reference). Film sample 80mm in TD x 18mm in MD
Cut out into a rectangle of the same size and weighs 500
It is attached to a smooth plate of g so that the surface on which the photosensitive layer is to be coated faces upward (Sample B). Furthermore, thread is attached to the center of this 18 mm side. After placing sample B on sample A, sample B
The yarn is fixed to the load cell via the pulley on the moving stage of the tensile tester. Lower the moving stage at a speed of 200 mm / min. The maximum load detected by the load cell at this time is obtained as the "squeak value". (9) Centerline Average Roughness (Ra) The calculation principle of Ra is based on the centerline average roughness defined in JIS-B0601 "Surface Roughness". The measurement is
This was performed using a universal surface profiler SE-3F manufactured by Kosaka Laboratory. (10) Coefficient of static friction between the inner and outer surfaces of the roll After storing the sample for 2 hours at 25 ° C and 60% RH, one of which was cut to 35 mm x 35 mm was used as a measuring needle, and the other sample was loaded with a load of 100 g. , 60 cm /
HEIDON made by Shinto Chemical Co., Ltd.
It was measured with a -14 type dynamic friction coefficient measuring machine.

Example 1 (1) Preparation of Base Film (A) 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 form a biaxial film having a thickness of 80 μm. In producing a stretched polyester film, as shown in FIG. 2, an infrared heater was installed as an auxiliary heating source on one surface of the longitudinal stretching zone (in this example, the surface in contact with the casting drum during casting: hereinafter referred to as CD surface). . (B) As shown in Table 1, silica having different particle diameters was contained in the PEN chip in an amount of 0.5% by weight and stretched in the same shape as above. (C) PBB1- (PEN / PET = 60/40 blend) above as an example of a polyester blend support
I made a film. PEN and PET pellets as the polyester used for the support 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. This polyester was stretched in the same manner as in (A) with some samples containing 0.5% by weight of silica.

(D) As a polyester having a glass transition temperature of 90 ° C. or higher, the above-mentioned PBC-2 (support composition NDCA
/ TPA / EG = 75/25/100 (mol%) copolymer) was prepared. This is terephthalic acid (TP) as a dicarboxylic acid using a stainless steel autoclave.
A) Dicytyl and 2,6-naphthalenedicarboxylic acid (ND
CA) Dimethyl, ethylene glycol (EG) as a diol were mixed in the above composition, and 0.025 mol of antimony trioxide (based on the acid component) was used as a catalyst to perform polycondensation by a transesterification method. Similarly, P
Ar (TPA / bisphenol A = 100/100 (m
ol%)) and poly (oxyisophthaloyloxy-2,
6-dimethyl isopropylidene 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. Some of these polyesters contained 0.5% by weight of silica and were stretched in the same manner as above.

The stretching temperature conditions for the above samples are as follows. PEN, PBB-1, PBC-2, PAr,
PMeAr has an extrusion temperature of 300 ° C. and a longitudinal stretching temperature (CD
Surface side) 140 ° C, transverse stretching temperature 130 ° C, heat setting 250 ° C
The film was formed in 6 seconds. On the other hand, PET has an extrusion temperature of 270 ° C., a longitudinal stretching temperature (CD surface side) of 100 ° C., a transverse stretching temperature of 110 ° C.
A film was formed by heat setting 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 8 and B-1 to
6, C-1 to 3 and D-1 to 5 were formed into a film. The thickness of the support thus formed is 80 μm. Of these, PMcAr (D-5) was not suitable for use as a silver halide photographic light-sensitive material because the transparency of the film was poor.

[0069]

[Table 1]

[0070]

[Table 2]

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 Among the above supports, the comparative examples A-1 to C-8, C-3 and D-3 were subjected to heat treatment B-1 to C-6, C-1 and C-2 before being subjected to heat treatment. 4, D
In Nos. 1, 2, and 4, after heat treatment, corona discharge treatment was performed on both surfaces of each, and then an undercoat layer having the following composition was provided on the high temperature surface side during stretching. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during 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 C-8, C-3 and D-3
In the comparative example, each surface was subjected to ultraviolet irradiation treatment before heat treatment, and then an undercoat liquid having the following composition was applied, dried at 120 ° C. for 2 minutes and then wound. Application amount is 10cc
Was / m ² . For the ultraviolet irradiation treatment, the apparatus shown in FIG. 1 was used and ultraviolet irradiation was performed under the above-mentioned stretching and heat setting conditions. Therefore, the irradiation time is 6 seconds and the irradiation conditions are 3 as described above.
Twelve KW high-pressure mercury lamps are arranged at a distance of 0.3 m from the film surface. These samples were used as A'-1 to 8, C'-3 and D'-3 comparative examples 1 ', respectively.
-1 to 1'-4, and coating of a photosensitive layer described below was performed in the same manner as above. Gelatin 1 part by weight Water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene dichloride 50 parts by weight P-chlorophenol 4 parts by weight

3) Coating of back layer A back layer having the following composition was coated on the surface opposite to the side on which the undercoat layer of the support after undercoating was 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]
Was applied to give a dry film thickness of 0.3 μm and dried at 90 ° C. for 1 minute. Samples B-1 to 6 and C-
For 1, 2, D-1, 2 and Comparative Examples 1-1 to 1-4, the coating liquid (B) for coating layer described below was further applied to give a dry film thickness of 0.1.
It was applied to have a thickness of μm and dried at 90 ° C. for 3 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 In addition, for samples A-1 to 8, C-3 and D-3, 4, Table 1 is described. The following coating solution (C) for a coating layer containing the matting agent is coated to a dry film thickness of 0.1 μm,
It was dried at 130 ° C. for 2 minutes. [Coating liquid for coating layer (C)] 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 Matting agent described in Table 1 0.05 parts by weight

4) Heat Treatment of Support In the above samples, A-1 to C-3, D-
For Nos. 3 and 4, after coating the back layer, B-1 to 6 and C-
Regarding 1, 2, D-1, 2 and Comparative Examples 1-1 to 1-4, the heat treatment was performed on the unprimed base samples under the conditions shown in Table 1. The heat treatment was carried out in the form of a roll after winding the undercoating surface on the outer circumference of a stainless steel core having a diameter of 30 cm. Comparative Example As a comparative example, in accordance with Table 1, the above-mentioned example which was not heat-treated was prepared. In addition, 1 on the core before heat treatment
A base of 2000 m in width of m is 50 m per minute under a tension of 10 kg.
The appearance of the roll at the time of winding and winding was evaluated. It is shown in Table 1 that if the end of the roll is misaligned by 5 cm or more, it is NG, and if it is less than that, it is OK. All the bases with a squeaky value of 10 g or less are too slippery and are NG.

Among the mechanical strengths of these supports, the most important bending elasticity was measured as the supports became thinner. The bending elastic modulus was measured by using a method called a ring method. That is, a sample having a width of 35 mm and slits parallel to the length direction was used to form an annulus having a circumference of 10 cm, which was placed horizontally, and this was deformed by 12 mm, and the load at the time of deformation was measured and used as a measure of the bending elastic modulus. . In this measurement, the undercoat layer was measured so that the undercoat layer was on the inner circumference of the ring, and the measurement environment was 25 ° C. and 60% RH. The results measured by these are shown in Table 1. PEN is 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.

5) Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the composition shown below is multilayer-coated to form a multilayer color photosensitive material A-1 to B-8.
.About.6, C-1 to 3, D-1 to 4, and 1-1 to 1-4 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.

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

Further, in order to improve storage stability, 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.

[0095]

[Table 3]

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

[0097]

[Chemical 7]

[0098]

[Chemical 8]

[0099]

[Chemical 9]

[0100]

[Chemical 10]

[0101]

[Chemical 11]

[0102]

[Chemical 12]

[0103]

[Chemical 13]

[0104]

[Chemical 14]

[0105]

[Chemical 15]

[0106]

[Chemical 16]

[0107]

[Chemical 17]

[0108]

[Chemical 18]

[0109]

[Chemical 19]

[0110]

[Chemical 20]

[0111]

[Chemical 21]

6) Sample Evaluation The photographic film samples thus prepared were evaluated for curling. The evaluation was performed according to the following procedure. 6-1) Core set The sample film was slit into a width of 35 mm and a length of 1.2 m. After humidity-controlling this at 25 ° C. and 60% RH overnight, the photosensitive layer was wound inside and wound on an 8 mm spool as shown in Table 1. This was placed in a sealed container, and heated at 50 ° C. for 24 hours or at 80 ° C. for 2 hours to be wound. This temperature condition is a core set condition corresponding to the curl when the former is stored at room temperature for 2 to 3 years and left, while the latter is a condition assuming that the film was put in the car in the summer. 6-2) 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.

[0113]

[Table 4]

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 Settlement 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

6-3) Evaluation of Film Properties after Heat Treatment The samples wound around the core and heat treated were evaluated for roll properties after the heat treatment. For evaluation, the sample after heat treatment was once rewound on another winding core, and a portion of 100 m in length was taken out for 1 m from the winding start of the first winding core and spread, and sagging, wrinkle-like or wrinkle-like deformation of the sample It was observed and evaluated according to the following criteria. A rank: No deformation B rank: Slightly wrinkled or wrinkled deformation observed C rank: Large wrinkled deformation Note that sagging, wakame or wrinkled deformation of the sample is shown in FIG. As shown in FIG. 3, sagging deformation occurs at the center of the sample, wakame deformation occurs at the end of the sample, and wrinkle deformation occurs over the entire surface of the sample.

7) Results The results are shown in Tables 1 and 2. When the core was set at 50 ° C. for 24 hours, no troubles due to winding occurred at any level subjected to the heat treatment of the present invention. On the other hand, all of Comparative Examples 1-1 to 5 which were not subjected to the heat treatment had troubles. Therefore, with respect to the film stored at room temperature, it is possible to effectively prevent troubles caused by winding the film by the heat treatment of the present invention. Furthermore, even assuming the conditions of automobiles in the summer, PEN and P with a glass transition temperature exceeding 90 ° C.
BB-1, PBC-2, and PAr are effective. When heat treatment is applied with a temperature difference during stretching, curling is reduced by heat treatment for about 6 hours, and even during core setting at 80 ° C for 2 hours No troubles. On the other hand,
In the case of no heat treatment, a fold occurred during the development treatment.
Furthermore, when PEN is used, the bending elastic modulus by the circular ring method is 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 winding mark that causes actual damage, and 8
There is an advantage that the support can be thinned to 0 μm.

PM having a glass transition temperature of 200 ° C. or higher
With eAr, a film with good transparency was not obtained, and it was not suitable for use as a photographic light-sensitive material. (D-5) Further, the roll properties after the heat treatment are those having a large squeaky value, that is, those having no matting agent and those having a small surface roughness (A-1, B-1, 2, C-1, In D-1), the flatness was deteriorated because wrinkles, wrinkles, and after-blocking occurred. Further, during winding, squeaks were generated, and therefore fine scratches were generated. Moreover, the particle size of the matting agent is large,
Samples with large surface roughness had a creaking value of 400 g or less on the inner and outer surfaces of the roll and did not deteriorate the roll shape, but samples with large surface roughness (A-4, B-6).
In such a case, it was too slippery to be rolled up neatly, or the graininess was deteriorated due to the appearance of the matting agent during printing. Other samples A-2 to 4 and B-3 satisfying the requirements of the present invention
For the samples of ~ 5, C-2 to 3, and D-2 to 4,
There was no particular problem of photographic property, and it could be preferably used as a silver halide photographic light-sensitive material. Also, similar results were obtained for the sample in which the undercoat layer was applied after the UV treatment.

Example 2 1) Preparation of sample (E) PEN chips were made to contain 0.5% of the matting agent under the conditions shown in Table 4, and as in Example 1, Table 4
The film was stretched and formed into a film under the conditions shown in. Table 4 on the back layer
The slip agent shown in 1 was applied according to the following formulation (D). Formulation (D) Lubricating agent 1 part by weight Xylene 500 parts by weight Then, heat treatment was performed in the same manner as in Example 1, and an undercoat and a back layer were further applied to prepare samples E-1 to E-8. (F) In the PEN support of Example 1- (A), the coating liquid (C) was applied in place of the coating liquid (C), and winding heat treatment was performed to obtain a sample F- as shown in Table 4. 1-6
Prepared. (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 Table 4 Sliding agent 0.5 parts by weight Table 4 Matting agent 0.05 parts by weight In the same manner as in Example 1, a photosensitive layer was coated on the above samples. Tables 4 and 5 show the above sample preparation conditions and evaluation results.

[0119]

[Table 5]

[0120]

[Table 6]

The following lubricants were used as the slip agent applied to the above samples.

[0122]

[Chemical formula 22]

2) Evaluation of Sample The sample thus prepared was evaluated in the same manner as in Example 1. However, all core setting conditions for evaluation of curling were performed at 80 ° C. for 2 hours.

3) Results The results are shown in Tables 4 and 5. In this embodiment, E-1 to
In all Nos. 8 and F-1 to 6, curl was reduced, and troubles during development processing were eliminated. In comparison with the rolls after the heat treatment, in the sample to which the slip agent was applied, the squeaky value between the inner surface and the outer surface of the roll was 400 g or less, and no wrinkle-like or wrinkle-like deformation and no blocking after-treatment occurred. This was also the case when combined with a matting agent. On the other hand, with respect to the sample to which the slip was not applied, the flatness of the roll after the heat treatment deteriorated, the creaking during the winding occurred, and the fine scratches occurred. From the above results, the effect of applying the slip agent of the present invention was observed.

Example 3 1) Preparation of sample (E) PEN chips 0.5% by weight of silica having an average particle size of 0.6 μm as a matting agent in the film at all levels.
And extruded at 300 ℃, 133 ℃
Longitudinally stretched 3.3 times at 130 ° C., then laterally stretched at 130 ° C. at 3.5 times to make a biaxially stretched base, and then heat set at 247 ° C. for 2 seconds to obtain a PEN film having a thickness of 85 μm. It was

2) Surface Treatment of Support All samples were subjected to UV treatment. The ultraviolet treatment was carried out by setting the temperature of the support at 200 ° C. and irradiating both sides of the support for 30 seconds from a distance of 20 cm using a 1 KW high pressure mercury lamp.

3) Coating of Back First Layer 3-1) Preparation of Conductive Fine Particle Dispersion (Tin Oxide-Antimony Oxide Composite Dispersion) It was carried out in the same manner as in Example 1 3-1). 3-2) Preparation and coating of the first layer of bag The coating was performed at 5 ml / m ² while changing the content of the conductive fine particle dispersion of the following formulation [A] with respect to all levels. 110 this
It was dried at ℃ for 3 minutes. [Formulation A] Dispersion liquid of conductive fine particles described in Table 6 1 part by weight of water Described in table 6 Methanol 〃 resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0.01 part by weight

4) Heat treatment of the support All the heat treatment was carried out by winding a back side of the stainless steel core having a diameter of 30 cm onto a base having a width of 1 m for 2000 m and then keeping the roll in a constant temperature bath at 115 ° C. I put it in and carried it out. At this time, a temperature sensor was put in the outer peripheral portion of the base, and when the base temperature reached 110 ° C., the heating switch of the constant temperature bath was turned off, and the base was allowed to cool to room temperature. Comparative Example As a comparative example, one not subjected to the above heat treatment was prepared according to Table 6.

[0129]

[Table 7]

[0130]

[Table 8]

5) Evaluation of rolls before and after heat treatment Winding before heat treatment Evaluation was carried out in the same manner as in Example 1, and the end portion when a base having a width of 1 m was wound around the winding core at a tension of 10 kg and a speed of 50 m / min for 2000 m. If the deviation is 5 cm or more, it is NG, and if it is less than that, OK
And Also in this method, the winding form was NG when the squeaky value, the dynamic friction coefficient, and the Ra value level G-5 of the present invention or more were within the ranges of the present invention. Roll shape after heat treatment It was carried out by the same method as 6-3) in Example 1. Also in this method, Levels G-2 to 4 of the present invention had a good surface condition.

6) Coating of undercoat layer On the surface opposite to the back surface, an undercoat liquid having the following composition was added in an amount of 10 ml /
m ^{2 was} applied and dried at 110 ° C. for 2 minutes. Gelatin 1 part by weight Distilled water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene chloride 50 parts by weight p-Chlorophenol 4 parts by weight

7) Coating of Back Second Layer The following coating liquid for coating layer was further coated on the coating layer of the first back layer so that the dry film thickness was 1 μm, and the coating was carried out at 115 ° C. for 3 days.
Dry for minutes. [Coating Layer Coating Liquid] 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 Silica particles (average particle size 0.2 μm) 0.01 parts by weight Polysiloxane 0.005 parts by weight C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (8/2 weight ratio) 0.01 parts by weight Dispersion (average particle size 20 μm)

8) Coating of photosensitive layer On the support obtained by the above-mentioned method, each layer having the same composition as in Example 1 of Japanese Patent Application No. 5-82 was coated in multiple layers to prepare a multilayer color photosensitive material.

9) Sample Evaluation The samples thus prepared were examined for curling according to 6-1) and 6-2) of 6) Sample evaluation of Example 1. However, all core setting was performed at 80 ° C. for 2 hours.
The results are shown in Table 6. In each of G-2 to G-4 of the present invention, curling was difficult to occur, and no processing trouble occurred. On the other hand, at the level of H-1 which has been subjected to heat treatment, trouble has occurred. By carrying out the present invention as described above, a polyester photographic film having a good surface condition and being hard to curl can be produced.

[0136]

By carrying out the present invention, there are provided a silver halide photographic light-sensitive material which is hard to curl and has strong mechanical properties and has no problem in flatness and photographic property, and a method for producing the same. Can be provided.

[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.

FIG. 3 is a perspective view showing a film after heat treatment of a sample wound around a winding core according to the present invention and a state in which the film is partially unraveled.

FIG. 4 shows a squeezing measurement apparatus of the present invention.

[Explanation of symbols]

 1 Film 2, 3 Longitudinal Stretching Roller 4 Cooling Roller 5 Infrared Heater 6 Preheating Horizontal Stretching Zone 7 Heat Fixing and Irradiation Zone 8 Cooling Zone 9 High Pressure Mercury Lamp 10 Reflector 11 Exhaust 12 Hot Air Supply 13 Cold Air Supply 14 Closing Frame 15 Winding 16 Film sample 17 Core 18 Seaweed deformation 19 Sagging deformation 21 Wrinkle deformation 21 500g plate with sample film attached 22 Sample film 23 Horizontally mounted sample stage 24 Pulley 25 Moving stage of tensile tester 26 Load cell 27 Tensile tester

Claims (10)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one surface of a polyester film support, the support being provided after the film formation and before the coating of the light-sensitive layer. A heat treatment in a roll form at a temperature of 50 ° C. or higher and a glass transition temperature or lower of the support, and a squeaky value between the front and back surfaces of the support during winding before the heat treatment is 10 g or more and 400 g or less. And a silver halide photographic light-sensitive material. 2. The average surface roughness of at least one side of the roll film before winding, before the heat treatment, is 0.01 μm to 5 μm.
2. The silver halide photographic light-sensitive material according to claim 1, which has a size of .mu.m. 3. At least one lubricant selected from organopolysiloxane, higher fatty acid and its derivative, higher alcohol and its derivative, and paraffin is contained on at least one surface of the roll before winding before the heat treatment. The silver halide photographic light-sensitive material according to claim 1 or 2, characterized in that. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the glass transition temperature of the polyester film support is 90 ° C. or higher and 200 ° C. or lower. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the dynamic friction coefficient between the outer surface and the inner surface of the roll at the time of winding before the heat treatment is 0.40 or less. 6. The heat treatment method for a polyester film according to claim 1, wherein the glass transition temperature of the polyester film is 90 ° C. or higher and 200 ° C. or lower. 7. 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. 8. The polyester film has a thickness of 50 μm.
m or more and 300 μm or less.
To 7. A silver halide photographic light-sensitive material described in any one of 1. 9. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester film support is polyethylene-2,6-naphthalenedicarboxylate. 10. A method for producing a silver halide photographic light-sensitive material according to any one of claims 1 to 9.