JP2840903B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and more particularly to a method of winding a support at a temperature of not higher than Tg + 100.degree. C. and not lower than Tg-50.degree. The present invention relates to a silver halide photographic light-sensitive material which is difficult to get loose and has excellent adhesion to an emulsion layer.

[0002]

BACKGROUND OF THE INVENTION Photographic materials are generally prepared by coating at least one photographic layer on a plastic film support. As the plastic film, a fiber-based polymer represented by triacetyl cellulose (hereinafter referred to as "TAC") and a polyester-based polymer represented by polyethylene terephthalate (hereinafter referred to as (PET)) are generally used. I have. Generally, photographic photosensitive materials include X-ray films,
A sheet-shaped film such as a plate making film and a cut film, and a typical roll film are 35 m
A color or black-and-white negative film which is housed in a patrone with a width of / m or less and is generally loaded into a camera and used for photographing. TAC is mainly used as a roll film support.
It is optically unlawful and has high transparency. There is one more excellent feature, which is that it has excellent properties in terms of curl removal after development.
In other words, the TAC film has a relatively high water absorbency as a plastic film as a feature derived from its molecular structure, so that the curl generated by being aged in the state of being wound as a roll film causes the molecular chains to be absorbed by the water absorption in the development process. The molecular chains that flow and become immobilized over time cause rearrangement. As a result, it has an excellent property that the curl once formed is eliminated. In a photographic photosensitive material using such a film having no curl recovery property such as TAC, when used in a roll state, for example, in a printing process for forming an image on photographic printing paper after development, a slip process is used. Problems such as scratches, defocusing, and jamming during transport will occur. On the other hand, PET films have been considered to be an alternative to TAC because of their excellent productivity, mechanical strength, and dimensional stability. However, curled curls are widely used as photographic photosensitive materials. , The handleability after development processing is poor, and the range of use has been limited despite the excellent properties described above.

In recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transport during photographing, the increase in photographing magnification, and the miniaturization of photographing apparatuses have been remarkably progressing. In that case, as a support for the photographic photosensitive material,
Properties such as strength, dimensional stability, and thinning are required. Further, with the downsizing of the photographing apparatus, the demand for downsizing the patrone has increased. Conventionally, in the 135 system, a patrone having a diameter of 25 mm has been used. However, the spool (core) is reduced to 10 mm or less, and at the same time, the thickness of the TAC support used in the current 135 system is reduced from 122 μm to 90 μm.
If the thickness is reduced to μm, the patrone can be reduced to a diameter of 20 mm or less. The first problem to achieve this is a decrease in mechanical strength due to thinning of the film. In particular, the bending elasticity decreases in proportion to the cube of the thickness. Silver halide photographic materials generally have a photosensitive layer dispersed in gelatin, and this layer causes shrinkage due to low humidity,
Generates toy curls. The support must have sufficient bending elasticity to withstand this contraction stress.

[0004] The second problem is a strong curl that occurs during storage over time due to miniaturization of the spool. In the conventional 135 system, the winding diameter becomes the smallest inside the patrone.
The winding diameter is 14 mm even for a six-image film. This is 10
Attempts to reduce the size to less than mm will result in significant curl, which will cause various problems. For example, when development processing is performed on a minilab automatic machine, the film is wound up because one end is fixed to the reader and the other end is not fixed. Cause. Further, the winding of the film is crushed by a roller in the mini lab, and "breaking" occurs.

[0005] A TAC or PET support which has been conventionally used as a support for achieving such a problem cannot provide satisfactory performance, and it is necessary to use a support made of a new polymer material.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material (hereinafter referred to as photographic material and photographic material) which has excellent mechanical properties, is hardly curled, and has excellent manufacturing suitability. Abbreviated).

[0007]

According to the present invention, there is provided a silver halide photographic material having at least one photosensitive layer on a polyester support, wherein the polyester support comprises naphthalenedicarboxylic acid and ethylene glycol. And the polyester film support is wound up in a roll at a temperature of Tg + 100 ° C. or lower and Tg−50 ° C. or higher, so that the temperature is substantially uniform from the core to the outside of the winding. This was achieved by a silver halide photographic material characterized in that the body was heat-treated. A description will be given of the winding measurement method used first and terms related thereto. (1) Core set The film is wound around the spool and rolled. (2) Core set curl The core set curl is applied in the length direction. The degree of curling is measured according to Test Method A of ANSI / ASC pH 1.29-1985, and 1 / R
[M] (R is the radius of the curl). (3) Absolute core set curl The core set curl of the photographic film before the winding improvement. (4) Controlled core set curl The core set curl of the photographic film after the curl improvement. (5) True core set curl (absolute core set curl)-(Controlled core set curl) (6) Curl reduction rate (true core set curl / absolute core set curl) x 1
(7) Glass transition temperature (Tg) The sample film 10 was measured using a differential thermal analyzer (DSC).
mg in a helium nitrogen stream at 20 ° C./min. When the endothermic peak appears at the arithmetic mean temperature or Tg of the temperature that begins to shift from the baseline and the temperature that returns to a new baseline. The temperature showing the maximum endothermic peak is defined as Tg.

[0008] There are two ways to achieve the two problems mentioned above: strong mechanical strength and low curl. The first method is a method in which TAC having curl recovery properties is modified to improve mechanical strength. The second method is
This is a method of preventing a polyester support represented by PET, which is excellent in mechanical strength, from being easily rolled up. Achieving this task in the former way is expected to be very difficult. That is, the thickness of the TAC support used in the current color negative photographic material is 122 μm, and when this is reduced to 90 μm, the curvature elasticity becomes 3 times the thickness.
Since it is proportional to the power, it falls to 40% of the 122 μm support. That is, it is necessary to achieve a support having a 2.5 times higher elastic modulus. Further, when the spool diameter is reduced to 10 mm or less, even the TAC having the winding recovery property cannot fully recover during the developing process, and the above-mentioned "processing unevenness" or "break" occurs. As described above, it is considered to be quite difficult to simultaneously solve the two problems of “improving the elastic modulus by 2.5 times” and “improving the curl recovery”.

On the other hand, when the latter method is intended to be achieved, for example, a bending elasticity equivalent to TAC of 122 μm can be achieved at 90 μm due to the inherently high elastic modulus when PET is used. Furthermore, polyethylene naphthalate (PE
When N) is used, the modulus of elasticity is higher than that of PET and 80 μm.
m can be reduced. So in the latter case,
It is only necessary to improve the winding of these supports, and the present inventors have conducted studies from this direction and arrived at the present invention.

As a method for making the polyester film hardly curled, a method described in JP-A-51-16358, that is, a glass transition temperature of 30 ° C. to 50 ° C.
A method of performing heat treatment at a lower temperature is known. However, there are some problems in actually adapting this method to industrial production. The biggest problem is how to heat the film. From the viewpoint of productivity, the film support is wound into a roll and heat-treated. However, since the heat transfer rate of the polyester is low, the temperature of the core increases to a predetermined temperature in about 2 to 3 days. And the production efficiency is greatly reduced. Further, there is also a problem in that when heated after winding at room temperature, the base shrinks and the base is swelled. In order to solve this problem, the present invention has found that the same effect as in JP-A-51-16358 can be obtained in a short time by heating the support before winding and then performing a predetermined heat treatment after winding. Was. According to the present invention, the time required for raising the temperature of the support in the past can be reduced from two to three days, and the same effect can be obtained in a shorter time than in the case where the temperature is kept constant by slower cooling. Was found to significantly improve production efficiency. At the same time, the occurrence of beveling can be prevented, and a uniform base can be obtained.

In the present invention, Tg + 100 ° C. or less Tg-5
0 ° C or higher temperature, more preferably Tg + 30 ° C or lower Tg
After being wound into a roll at a temperature of -30 ° C or higher, it is heat-treated. When the winding temperature is higher than Tg, the effect of preventing the curling is greater, but the elastic modulus which is too high is lowered, and the winding becomes difficult. It is desirable to wind at Tg + 100 ° C. or lower, more preferably Tg + 30 ° C. or lower. on the other hand,
If the film is wound at a temperature of Tg-50 ° C. or lower, a sufficient effect cannot be obtained in a heat treatment performed later because the temperature is too low. Therefore, the winding temperature is Tg−50 ° C. or more, more preferably Tg
It is preferably performed at a temperature of at least g-30 ° C.

It is easy to wind up the support at such a high temperature. For example, since the polyester support is heat-set at 200 ° C. in the final process of film formation, the support may be cooled to a temperature according to the present invention with a cool air or a cooling drum and then wound. Also, after the undercoat or the back layer is applied, the support usually comes out through the drying zone at 100 ° C. to 200 ° C. Therefore, if necessary, the temperature of the support may be lowered by a cooling drum or cool air, or the heat may be applied. After being heated by passing through a drum, it may be wound up. Further, the base once lowered to room temperature can be easily raised to a predetermined temperature simply by passing it through a warm air zone or contacting a heat roll. As described above, the temperature of the base can be adjusted to the winding temperature of the present invention, and the base can be easily wound. It is desirable to wind the support at a high speed so that the heated support is not allowed to cool as much as possible. Further, it is more preferable to provide a blowing outlet for warm air such as an infrared heater near the winder to wind up while heating.

When the film is wound in this manner, the desired temperature can be almost uniformly maintained from the core to the outside of the winding in the wound state. On the other hand, a PET support having a thickness of 100 μm and a width of 1 m wound up to a diameter of 1 m was heated from room temperature to
It takes more than 2 days to heat to 00 ° C.
A temperature difference of 20 ° C. or more occurs between the winding core and the outside of the winding. Further, the base is also shrunk by heat shrinkage, and the flatness is reduced. As described above, the present invention enables an efficient and homogeneous heat treatment to be performed in a very short time without deteriorating the flatness of the base.

The support wound in this manner is kept at a temperature of not more than Tg and not lower than room temperature, more preferably not more than Tg and not less than room temperature, more preferably at a temperature of not more than Tg-5 ° C. and not less than Tg-40 ° C. for not less than 0.1 hour and not more than 1500 hours. Hereinafter, more preferably, 2
Heat treatment is performed for at least 200 hours. Such Tg
The following heat treatment is the same as the method described in JP-A-51-16358, and is intended to impart a stable structure to the molecule at Tg or less to make it difficult for the molecule to flow. On the other hand, if the heat treatment is performed at Tg or more, the molecule becomes unstable due to intense Brownian motion of the molecule, and the molecule easily flows and is easily curled. Therefore, this heat treatment needs to be performed at a temperature equal to or lower than Tg, and even if the film is wound at a temperature equal to or higher than Tg, it is necessary to cool the heat treatment to a temperature equal to or lower than Tg. However, the formation of a stable structure by this heat treatment is preferably performed at a temperature as high as Tg or lower, and more preferably at a temperature as high as possible because the structure is formed more quickly. On the other hand, near Tg, unstable structure formation due to Brownian motion has already started. For this reason, the heat treatment of the present invention is carried out at Tg or lower at room temperature or higher, more preferably at Tg-5.
Performing at a temperature range of 0 ° C. or less, Tg-40 ° C. or more,
More preferred.

In this way, Tg + 100 ° C. or less Tg
After winding at a temperature of −50 ° C. or higher, Tg or lower, when heat treatment is performed at room temperature or higher, the support is formed into a roll,
The heat treatment can be performed in a significantly shorter time than when the temperature is raised to a predetermined temperature, and then the heat treatment is performed.In addition, since the temperature difference between the core and the outside of the winding is small, a more uniform heat treatment can be performed. Can be achieved. Furthermore, it is possible to prevent the occurrence of curling, bulges, and the like due to the heat shrinkage of the base, which have occurred when heating was performed at room temperature or the like. The heat treatment time must be at least 0.1 hour, more preferably at least 2 hours, in order to obtain a sufficient effect. On the other hand, the effect after 200 hours begins to saturate and completely saturates after 1500 hours. Therefore, the heat treatment time is 1500 hours or less, more preferably 200 hours or less.

It has been newly found that such a heat treatment at a temperature of Tg or lower is more accelerated when the heat treatment is performed while gradually cooling than when the heat treatment is performed at a constant temperature. Slow cooling rate is -0.1 ° C / h
It is necessary to be at least r and at most -20 ° C / hr. −
At a temperature of 20 ° C./hr or less, the cooling is too fast and a sufficient effect cannot be obtained. On the other hand, when the temperature is -0.01 ° C / hr or less, a sufficient slow cooling effect cannot be obtained as in the case of the constant temperature. Therefore, it is not less than -0.01 ° C / hr and not more than -20 ° C / hr, more preferably not more than -3 ° C / hr and not more than -0.2 ° C / hr.
r or more. In addition, the slow cooling is performed at Tg or more for the above-mentioned reason.
Since it has no effect, it must be performed at Tg or less.

The support thus heated is gradually cooled. The easiest method of slow cooling is to leave the support wound up in a roll form at room temperature and cool slowly. In this case, when a PET support having a thickness of 100 μm and a width of 1 m is wound to a diameter of 1 m, it is required that the temperature be from about 100 ° C. to room temperature.
It is possible to cool slowly over a period of days. However, in this case, there is a disadvantage that the temperature near the outermost layer tends to decrease more than the core. In such a case, it is possible to perform a more uniform heat treatment on the outer peripheral portion and the core by winding the heat insulating material around and gradually cooling the heat insulating material. In order to perform a more uniform heat treatment, the support heated by the above-described method is placed in a thermostat at a temperature to be subjected to the heat treatment, and the inside of the thermostat is cooled at a desired cooling rate. According to this method, it is possible to gradually cool at a predetermined cooling rate.

The roll of the support that has been slowly cooled may be cooled to room temperature as it is, or may be rapidly cooled to a predetermined temperature or room temperature from the slow cooling stop temperature. As a method of quenching, a method of contacting with a cooling roll while rewinding the roll, a method of sending cool air to cool, and the like can be used.

The effect of the heat treatment described above is as follows.
Disappears when exposed to temperatures above g. Therefore, when heat treatment is performed before the surface treatment of the base and the application of the undercoat layer or the back layer, it is necessary to perform such treatment or application so as not to exceed Tg. It must be performed before this heat treatment. Since the processing temperature of the present invention is a condition sufficient to decompose the components of the emulsion layer, it is preferable to perform the processing before coating the emulsion.

Such a heat treatment effect by slow cooling is effective for a polyester film, but is particularly effective for a polyester support having a Tg of more than 90 ° C. This is because the effect of the present invention disappears when exposed to a temperature exceeding Tg, and in a car under summer sunshine, the temperature rises to nearly 90 ° C, so that the polyester support has a Tg of 90 ° C or more. Is more preferred. Further, at present, there is no transparent polyester having versatility and having a Tg of 200 ° C. or more. For example, poly (oxyisophthaloyloxy-2,6
-Dimethyl-1,4-phenyleneisopropylidene-
3,5-dimethyl-1,4-phenylene) has a Tg of 225 ° C., but is not transparent. Therefore, the polyester of the present invention desirably has a Tg of 90 ° C or more and 200 ° C or less.

The polyester having such a Tg is as follows:
It is formed from a dibasic acid and a diol as follows. 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, tetrachlorophthalic anhydride, 3,6-
Endomethylene tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid,

[0022]

Embedded image

[0023]

And the like. Usable diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 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, resorcinol, hydroquinone, 1,4
-Benzene dimethanol,

[0025]

[0026]

Further, if necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl-containing compound or an acid-containing compound may be copolymerized. In the polyester of the present invention, a compound having both a hydroxyl group and a carboxyl group (or an ester thereof) in the molecule may be copolymerized.

[0028]

Of these diols and polyesters composed of dibasic acids, more preferred are polyethylene, 2,6-dinaphthalate (PEN), polyacrylate (PAr), and polycyclohexanedimethanol terephthalate (PCT). And dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), and paraphenylenedicarboxylic acid (PPDC), as a diol, ethylene glycol (EG), cyclohexane dimethanol (CHD)
M), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP) and parahydroxybenzoic acid (PHB) as a hydroxycarboxylic acid.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA). Among them, naphthalenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (a mixture molar ratio of naphthalenedicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 to 1.0: 0, 0.
5: 0.5 to 0.8: 0.2 is more preferred. ), A copolymer of terephthalic acid and ethylene glycol and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, more preferably 0.5: 0.5 0: 0.9 is preferable), isophthalic acid, paraphenylenedicarboxylic acid, copolymer of terephthalic acid and ethylene glycol (the molar ratio of isophthalic acid to paraphenylenedicarboxylic acid is 0.1 to 0.1 when terephthalic acid is 1). 10.
0, 0.1 to 20.0, and more preferably each of 0.
2 to 5.0, preferably 0.2 to 10.0), naphthalenedicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol to 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 to biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1: 0.9 to 0.2. 7: 0.3), parahydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of parahydroxybenzoic acid and ethylene glycol is 1: 0 to 0.1:
0.9 is preferable, and 0.9: 0.1 or more is more preferable.
0.2: 0.8) and PEN and PET
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable,
5: 0.5 to 0.8: 0.2 is more preferable), PET
And a polymer blend such as PAr (composition ratio is preferably 0.6: 0.4 to 0: 1.0, more preferably 0.5: 0.5 to 0: 0.9).

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

The polymer blend of the polymer thus obtained is described 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.

Next, preferred specific examples of the compound of the polyester (B) used in the present invention are shown, but the present invention is not limited thereto. Examples of polyester compounds ・ Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C PCT: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) ) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Copolymer (() indicates 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 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 ° C

All of the above-mentioned polyesters have a higher curvature modulus than TAC, and can achieve the original purpose of thinning the film. However, among these, PEN has the strongest bending elasticity, and by using this, it is possible to reduce the film thickness required for TAC from 122 μm to 80 μm. The thickness of these polymer films is 50 μm or more and 300 μm or less.
No transparent polymer film having a bending elasticity that can withstand shrinkage of the photosensitive layer at 50 μm or less does not exist, and at 300 μm or more, there is no point in using a thin-wound spool.

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

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

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

When these polymer films are used for a support, since all of these polymer films have a hydrophobic surface, a photographic layer (for example, photosensitive halide) composed of a protective colloid mainly composed of gelatin is provided on the support. It is very difficult to firmly adhere the silver emulsion layer, the intermediate layer, the filter layer, etc.). Conventional techniques that have been attempted to overcome such difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. , A mixed acid treatment, an ozone oxidation treatment, etc., a surface activation treatment, etc., followed by direct application of a photographic emulsion to obtain an adhesive force, and (2) once these surface treatments, or without surface treatment, There are two methods: a method in which an undercoat layer is provided and a photographic emulsion layer is coated thereon. (See, for example, US Pat.
8,241, 2,764,520, 2,86
No. 4,755, No. 3,462,335, No. 3,47
5,193, 3,143,421, 3,50
1,301, 3,460,944, 3,67
No. 4,531, British Patent No. 788,365, and No. 80
4,005, 891,469, JP-B-48-43
122, 51-446, etc.).

[0038]

[0039]

[0040]

Various gelatin hardeners can be used in the underlayer of the present invention. Gelatin hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And the like. In the underlayer according to the present invention, S
Inorganic fine particles such as TiO ₂ , TiO ₂ , matting agent or polymethyl methacrylate copolymer fine particles (1 to 10 μm)
m). In addition, various additives can be contained in the undercoat liquid as needed. Examples include surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first layer of the undercoat is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol in the undercoat liquid at all. However, if desired, the above-mentioned etching agent may be contained in the undercoat.

[0042]

The binder of the back layer may be a hydrophobic polymer or a hydrophilic polymer used for the underlayer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a lubricant, a matting agent, a surfactant, a dye, and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, for example, a carboxylic acid and a carboxylate as an anionic polymer electrolyte,
A polymer containing a sulfonic acid salt, for example,
No. 17, JP-B-46-24159, JP-A-51-30
No. 725, JP-A-51-129216 and JP-A-55-129216.
No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
No. 3, JP-A-48-91165, and JP-B-49-245.
No. 82, for example. Also, ionic surfactants are anionic and cationic, and are described in, for example, JP-A-49-85826 and JP-A-49-33630.
No., US 2,992,108, US 3,206,31
2, JP-A-48-87826, JP-B-49-1156
7, JP-B-49-11568, JP-A-55-708
No. 37 and the like. Most preferred as the antistatic agent of the back layer of the present _{invention, ZnO, TiO 3, SnO 2} , Al 2 O
₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃
And fine particles of at least one kind of crystalline metal oxides or composite oxides 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 0.0
It is desirable to set it to 1 to 0.7 μm, particularly 0.02 to 0.5 μm.

The method for producing the fine particles of the conductive crystalline metal oxide or composite oxide used in the present invention is described in JP-A-56-143430 and JP-A-60-258541.
It is described in detail in the specification of the issue. First, metal oxide fine particles are produced by firing, and heat treatment is performed in the presence of a heteroatom for improving conductivity. Second, a heterogeneous method for improving conductivity when producing metal oxide fine particles by firing is used. A method of coexisting atoms and a third method of introducing oxygen vacancies by lowering the oxygen concentration in the atmosphere when producing fine metal particles by firing are easy. Examples of containing heteroatoms include Al and In for ZnO, Nb and Ta for TiO ₂ , and Sb, Nb and halogen elements for SnO ₂ . The addition amount of the hetero atom is 0.01 to
A range of 30 mol% is preferred, but 0.1 to 10 mol%
Is particularly preferred.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be any of black and white colors. Here, a color silver halide photographic material will be described. The light-sensitive material of the present invention only needs to have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There is no particular limitation on the number of layers and the order of the non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as intermediate layers of the respective layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer has a structure as described in JP-A-61-43.
No. 748, No. 59-113438, No. 59-1134
No. 40, No. 61-20037, No. 61-20038, and couplers, DIR compounds, and the like described in the specification, and may contain a color mixture inhibitor as usually used. . A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent 1,121,4.
No. 70 or British Patent No. 923,045;
Nos. 7-112751, 62-200350, 62
-206541, 62-206543, 56-
25738, 62-63936, 59-202
No. 464, Japanese Patent Publication No. 55-34932, and No. 49-154
No. 95. Silver halide grains are
Those having regular crystals such as cubes, octahedrons, and tetradecahedrons, those having irregular crystal forms such as spheres and plates, those having crystal defects such as twin planes, or the like. It may be a composite type.

[0046]

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

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

[0049]

[0050]

[0051]

[0052]

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

[0054]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Example 1 1) Preparation of Support The following supports A to C were prepared by the method described below. Support A (polyethylene naphthalate (PEN): thickness 40 μm, 80 μm, 122 μm) Support B (polyethylene terephthalate (PET): thickness 90 μm) Support C (triacetyl cellulose (TAC): thickness 1)
Support A: 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and Diaresin (manufactured by Mitsubishi Chemical) as a dye having a thickness of 80 μm and an absorbance at 400 nm of 0.
And dried by a conventional method.
After melting at ℃, extruded from T-die at 3.3 ℃ at 140 ℃
And then stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds.
A film of 0,122 μm was obtained. Support B: A commercially available polyethylene terephthalate polymer was biaxially stretched and heat-set according to an appropriate method to obtain a film having a thickness of 90 μm. Support C: triacetylcellulose was subjected to ordinary solution casting by methylene chloride / methanol = 82 wt ratio,
TAC concentration 13% Plasticizer TPP / BDP = 2/1 (here, TPP; triphenyl phosphate, BDP: biphenyl diphenyl phosphate) was prepared by a band method of 15 wt%.

2) Heat treatment of the support The supports A and B formed by the above-mentioned method were subjected to a heat treatment by the method shown in Table 1 when the film was wound after the film was formed.

[0056]

[Table 1]

[0057]

[Table 2]

In the heat treatment, a heating roller was attached immediately before the winding machine at the time of film formation, and the support was heated so as to be in contact with the heating roller for about 1 second. The surface of the wound roll was measured with a contact thermometer, the temperature of the heated roll was controlled, and the winding temperature was set to a predetermined temperature. The rolled support is 1m wide and 5000 long
m was wound around a winding core having a diameter of 30 cm such that the undercoat layer became an upper winding. This was placed in a constant temperature room and gradually cooled under the conditions shown in Table 1-1. In addition, as a comparative example, the same length and similarly wound at room temperature were put in a 105 ° C.
After winding at 5 ° C. by the above method, the film was put in a thermostat at 105 ° C. for comparison. The result is shown in FIG. As described above, according to the method of the present invention, both the core and the outside
However, if the roll at room temperature is to be heated, the core does not reach 105 ° C. even after two days or more, and a large temperature difference occurs between the core and the outside of the roll. It turns out that it has been heat-treated. Furthermore, when the present invention was compared with the case where heating was performed from room temperature, as shown in Table 1, the former showed that the smoothness of the base was maintained after the heat treatment, whereas the latter method showed that Winding or the like has occurred. This is considered to be due to heat shrinkage caused by heat treatment after winding the base at room temperature, and furthermore, a difference in heat shrinkage due to a temperature difference between the outer winding side and the inner winding side of the roll. After the heat treatment, the most important bending elasticity was measured among the mechanical strengths of these supports as the support became thinner. The measurement of the curvature modulus was performed using a method called a ring method. That is, a ring having a circumference of 10 cm was formed from a sample having a width of 35 mm and slit in parallel with the length direction, and this was placed horizontally, and the load when this was deformed by 12 mm was measured and used as a measure of the bending elastic modulus. In this measurement, the measurement was performed with the undercoat layer being the inner circumference of the ring.
C. at 60% RH. Table 1 shows the measurement results. PEN is 80 μm and PET is 90 μm, showing a bending elastic modulus substantially equivalent to TAC of 122 μm.
This value did not change even when the heat treatment of the present invention was performed. As shown in A-14 and A-15, when the thickness of PEN was increased to 122 μm as in the case of TAC, it was found that the bending elasticity was at least three times that of TAC.

3) Coating of Undercoat Layer Each of the supports A and B was subjected to a corona discharge treatment on both surfaces thereof, and then provided with an undercoat layer having the following composition. In the corona discharge treatment, a 30 cm wide support is treated at 20 m / min using a solid state corona treatment 6 KVA model manufactured by Biller. At this time, the processing target is 0.37 based on the current and voltage readings.
KV · A · min / m ² was processed. 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 An undercoat layer having the following composition was provided on support C. Gelatin 0.2g Salicylic acid 0.1g Methanol 15cc Acetone 85cc Formaldehyde 0.01g

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

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

5) Coating of Photosensitive Layer On the support obtained by the above method, layers having the following compositions were applied in a multi-layered manner, and multilayer color light-sensitive materials A-1 to A-17 and B-
1-2 and C-1 were prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

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

Second layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

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

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

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

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

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

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

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

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

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

12th layer (medium speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

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

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

15th layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

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

[0079]

[Table 3]

In Table 2, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to F were prepared according to the examples in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin 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 using a high-pressure electron microscope.

[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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6) Sample evaluation Photographic film sample A-16 prepared in this manner
Was evaluated for winding. The evaluation was performed according to the following procedure. 6-1) Core Set The sample film was slit to a width of 35 mm and a length of 1.2 m. This was humidified overnight at 25 ° C. and 60% RH, and then the photosensitive layer was wound inside and wound on an 8 mm spool. This was placed in a sealed container and heated at 80 ° C. for 2 hours to form a roll. This temperature condition is a condition assuming that a film was placed in a car during the daytime in summer. 6-2) Development processing and curl measurement After the film wound under the above conditions was allowed to cool in a room at 25 ° C. overnight, a sample film was taken out from the sealed container, and was taken out of an automatic developing machine (Minilab FP). -550
B: Fuji Photo Film)
The curl was measured using a curl plate at 60% RH. The developing conditions are as follows.

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

6-3) Results The results are shown in Tables 1-1 and 1-2. The curl recoverability is greatly improved when A-1 which has been subjected to the heat treatment and A-3 which has been subjected to the heat treatment of the present invention are compared. On the other hand, when the heat treatment is performed after the roll has been wound at room temperature, as shown in A-2, the winding and the sticking have occurred after the heat treatment. In addition, heat transfer is slow, heat treatment is not sufficiently performed inside, and the curl reduction rate is low. For this reason, the rear end is bent. The temperature during winding is Tg + 100 ° C or lower, Tg-50 ° C or higher,
That is, in the case of PEN, the temperature needs to be 219 ° C. or lower and 69 ° C. or higher. If the temperature is higher than Tg + 100 ° C., as shown in A-4, the modulus of elasticity of the base decreases, and the base cannot be wound. On the other hand, at A-5 of Tg + 100 ° C., the film can be wound up, and the effect of curl reduction is sufficiently obtained. If the winding temperature is lower than Tg-50 ° C., as shown in A-8, a sufficient curling reduction effect cannot be obtained.
A-7 at 50 ° C or higher has a sufficient curling reduction effect,
No processing unevenness or breakage occurs. These heat treatments are further promoted by slow cooling. The case where the temperature is gradually cooled from 115 ° C to 95 ° C (A-6) and the case where the same temperature is maintained at 105 ° C which is the average temperature for the same time (A-3) are compared. The former has a greater curling reduction effect. The slow cooling temperature is -0.01 ° C /
It is desirable that the heating time is at least hr and at most -20 ° C / hr. -20 ° C / h
Above r, although processing unevenness and breakage do not occur as shown in A-12, curling is more likely to occur than A-13 which is kept constant at the average temperature of A-12 and processed for the same time.
On the other hand, in the case of A-11 at -20 ° C./hr or less, curling is less likely to occur than in the case of A-12 at a constant temperature. On the other hand, at -0.01 ° C./hr or less, the curl value becomes the same as that of the heat treatment (A-3) at a constant temperature as shown in A-9, and the effect of slow cooling is not seen. On the other hand, 0.
In the case of A-10 at a temperature of 01 ° C./hr or more, curling is less likely to occur due to slow cooling than in the case of A-3. Slow cooling needs to be performed to Tg or less. A where slow cooling was stopped at Tg or more
In the case of -15, the winding is too bad to cause breakage and uneven processing. On the other hand, A-14 cooled slowly to Tg or less provides a sufficient curl reduction effect. Next, the thickness of the support is desirably 50 μm or more and 300 μm or less. If it is less than 50 μm, the value of the ring method becomes 1/5 or less of TAC 122 μm as shown in A-17, and a strong toy-like curl due to shrinkage of the photosensitive layer occurs under low humidity. On the other hand, in the case of A-16 having a size of 50 μm or more, although a toy-like curl occurs, it is at a level at which there is no practical problem. If the film thickness is 300 μm or more, the cartridge cannot be miniaturized, which deviates from the object of the present invention. In addition, Tg is 9
With PET at 0 ° C. or lower, the curl reduction effect by such heat treatment cannot be obtained as shown in A-18. As described above, the bending elasticity equivalent to that of PET of 90 μm was achieved with PEN at 80 μm, and the heat treatment of the present invention made it hard to be rolled, so that the roll was able to be achieved and the mechanical strength exceeded TAC.

Example 2 1) Preparation of photosensitive material The polyester used for the support was PEN, PET, PA
r) The pellets of PCT were previously dried at 150 ° C. for 4 hours under vacuum, kneaded and extruded at 280 ° C. using a twin-screw kneading extruder at a mixing ratio shown in Table 3-1 to prepare pellets. This polyester was formed into a film in the same manner as in PEN of Example 1. This was further coated with an undercoat layer and a back layer according to the formulation of PEN in Example 1. Thereafter, the heat treatment was performed under the conditions shown in Table 2. This was evaluated in the same manner as in Example 1 by using the ring method, and the curvature modulus was evaluated.
In addition, a photosensitive layer was further applied according to Example 1 to prepare Samples D-1 to D-20.

2) Evaluation of Sample The photographic film B-1-12 thus produced was evaluated for winding in the same manner as in Example 1. At the same time, sensitometric evaluation was performed according to a conventional method, and the fluorescence emitted from the support was evaluated. PET that does not emit fluorescence
× compared with 3% or more in the median concentration compared with the sensitometry of,
The following were evaluated as ○. 3) Results The results are shown in Tables 3-1 and 3-2.

[0101]

[Table 4]

[0102]

[Table 5]

Even in such a polymer blend system, if the Tg exceeds 90 ° C., the effect of the present invention can be obtained. That is, even if the heat treatment is performed at a constant temperature after heating and winding as in B-1 to B-3, the same effect can be obtained by gradually cooling after heating and winding as in B-6 to 8, and It is hard to stick and there is no trouble during development processing. On the other hand, B-4, 5, B-
When the Tg is 90 ° C. or lower as in the cases of 9 and 10, there is no effect in any of the methods. Also, PEN1 like B-1 and B-6
At 00%, fluorescence was slightly generated, but by blending about 30% of PET as in B-2 and B-5, it was almost reduced to below the lower detection limit. Such effects can be obtained not only in the PEN / PET blend but also in the PCT / PAr blend. B-
11 and 12. That is, since the Tg is 90 ° C. or higher, it is possible to obtain a good support that is not easily rolled up by the heat treatment of the present invention.

Example 3 1) Preparation of photosensitive material For a polyester having a glass transition temperature of 90 ° C. or higher, an autoclave made of stainless steel was used. Dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate were used as dicarboxylic acids, and ethylene glycol was used as a diol. EG),
Bisphenol A (BPA) and cyclohexane dimethanol (CHDM) were mixed in the composition shown in Table 4, and 0.025 mol of antimony trioxide (based on the acid component) was used as a catalyst.
And polycondensation was carried out by a transesterification method. The polyester thus synthesized was formed into a film in the same manner as in PEN of Example 1. This was further subjected to a heat treatment after the application of the undercoat layer and the application of the back layer according to Example 1. In the same manner as in Example 1, the bending elastic modulus was evaluated by the ring method.
The photosensitive layer was coated thereon in accordance with Example 1 to obtain a photographic film sample C-8.

2) Sample evaluation The photographic film sample C1-8 thus prepared.
Was evaluated for winding in the same manner as in Example-1.

[0106]

[Table 6]

[0107]

[Table 7]

As shown in C-1 to C-5, NDCA / T
PA / EG copolymers having a Tg of more than 90 ° C. can have the effect of lowering the winding and improving the adhesion by the heat treatment of the present invention, while the Cg having a Tg of 90 ° C. or less can be obtained. -4,5
Did not achieve these effects. In addition, as shown in C-6 to 8, in the TPA / EG / CHDM / BPA system, those having a Tg of 90 ° C. or more also exhibited the effects of the present invention. Thus, the presence or absence of the effects of the present invention depends on Tg in the case of a polyester-based support, and the presence or absence of the effects can be divided depending on around 90 ° C.

[0109]

By using a polyester support which has been subjected to a heat treatment at a temperature not lower than Tg and not lower than room temperature and a heat treatment not lower than room temperature and not lower than Tg for not shorter than 0.1 hours and not longer than 1500 hours, the roll can be wound. A silver halide photographic light-sensitive material which is hard to stick and excellent in suitability for production is obtained.

[Brief description of the drawings]

FIG. 1 shows a core portion in which a support wound in a roll shape is heated from room temperature and a case in which the support is wound up while being heated.
This shows the temperature change outside the winding.

Claims (4)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive layer on a polyester support, wherein the polyester support is a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main raw materials. The polyester support was treated with Tg (glass transition point) +1
A silver halide photographic light-sensitive material, wherein the support is heat-treated without being cooled, while the temperature is substantially uniform from the winding core to the outside of the winding at a temperature of not more than 00 ° C and not less than Tg-50 ° C. . 2. The method according to claim 1, wherein the heat treatment is performed after winding the polyester support.
Tg at a rate of 0.01 ° C / hr or more and -20 ° C / hr or less
2. The silver halide photographic material according to claim 1, wherein the material is gradually cooled to a temperature not lower than room temperature. 3. The silver halide photographic material according to claim 1, wherein the polyester support has a Tg of 90 ° C. or more and 200 ° C. or less and a thickness of 50 μm or more and 300 μm or less. 4. A polyester support comprising polyethylene-
4. The silver halide photographic light-sensitive material according to claim 1, which is 2,6-naphthalenedicarboxylate.