JPH10274825A - Base body for long-length photographic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base body for a long-length photographic film which consists of a polyester comprising ethylene-2,6-naphthalate units and ethylene terephthalate units and does not produce wrinkles when heated. SOLUTION: This base body consists of a long-length polyester film having repeating units comprising 70 to 90 mol% ethylene-2,6-naphthalate units and 10 to 30 mol% ethylene terephthalate units, and having 110 to 128 μm film thickness. The dimensional changes of the film in the width direction and in the longitudinal direction ranges -0.6 to 0.6% at 180 deg.C and -0.5 to 0.5% at 120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is widely used as a silver halide photographic film for general cameras.
35m or brownie type photographic film width is 35m
The present invention relates to a photographic film support which can be suitably used for long photographic films having a length of at least m.

[0002]

2. Description of the Related Art In general, typical examples of a silver halide photographic light-sensitive material (photographic film) include a sheet-shaped film such as an X-ray film, a plate-making film and a cut film, and a roll-shaped film. There are things. A typical roll film is a 135-type color film or a black-and-white negative film, which is loaded into a general camera and used for photographing, and is stored in a patrone with a width of 35 mm. For example, 120-type and 220-type). Conventionally, a cellulose triacetate (TAC) film has been used as a support for a 135 type or brownie type film. The TAC film has no optical anisotropy and high transparency, and also has excellent curl-removing properties after development processing, and has good properties as a photographic support.

On the other hand, in response to a demand for miniaturization of a camera or a miniaturization of a patrone, thinning of a photographic support has been studied and has already been put to practical use. At that time, the use of the TAC was also studied, but there was a problem that if the TAC was thinned, the strength required for the photographic support was not satisfied. Therefore, high strength polyethylene terephthalate (PE)
T), polyethylene-2,6-naphthalate (PEN)
The study was advanced using polyesters such as. When a thin film is made of PET which has been conventionally used for a sheet-like film, the obtained film has a problem that curling due to curling is liable to occur. Since the PEN exhibited excellent properties, a thin film was realized using this PEN (EP0606070A1, JP-A-7-72584). This PEN film is used as a support for a new camera system, the Advanced Photo System (APS).

On the other hand, the above-mentioned TAC film is used as a support for a conventional 135 type or brownie type film. Since this TAC film is obtained by dissolving cellulose triacetate in an organic solvent such as methylene chloride, casting the resulting solution on a support such as a metal belt, and drying, the problem is that the working environment is easily contaminated. There is. In order to avoid the above-mentioned problem of the working environment, using the polyethylene-2,6-naphthalate (PEN),
A study was also conducted in the direction of producing a conventional 135 type or brownie type film support. However,
The support for 135 type or brownie type films is relatively thick (around 120 μm) to maintain compatibility with the systems conventionally used for these photographic films.
When the PEN film is used as such a support, there is a problem that troubles are apt to occur at the time of automatic loading and automatic winding of the film on the camera.

[0005]

SUMMARY OF THE INVENTION The present inventors have proposed that a PEN film can be used as a support for a 135 type or brownie type film, that is, a film having a thickness of 1%.
In order to obtain a film support in which the above problem does not occur in the range of 10 to 128 μm, various studies were made.
As a result, by using terephthalic acid together with 2,6-naphthalenedicarboxylic acid as a dibasic acid component forming a polyester (copolymer), or by mixing two or more kinds of polyesters having such a composition. As a result, it became clear that physical properties (eg, core set curl value, loop stiffness) suitable for a photographic film support were obtained, and that the support could be used as a 135 type or brownie type film support. The present inventors have already applied for such a photographic film support (Japanese Patent Application No. 8-113256, Japanese Patent Application No. 8-18).
0071, Japanese Patent Application No. 9-25921).

[0006] Such a photographic support is usually provided with a subbing layer thereon to improve the adhesion of the photographic emulsion layer. The inventors of the present invention have clarified that when a coating liquid for forming an undercoat layer is applied on a film obtained from the above polyester and dried, wrinkles are easily generated. In particular, this problem of wrinkling is likely to occur when the solvent of the coating liquid for forming an undercoat layer contains water as a main component, because the drying temperature must be increased.

An object of the present invention is to provide a support for a long photographic film which can be produced without using a solvent. An object of the present invention is to provide ethylene-
An object of the present invention is to provide a support for a long photographic film which is free from wrinkles due to heating made of a polyester comprising 2,6-naphthalate units and ethylene terephthalate units. It is a further object of the present invention to provide a support for a long photographic film which is hardly curled in curl, has excellent handleability, and does not generate wrinkles when heated.

[0008]

The cause of the wrinkles is as follows.
According to the study of the present inventors, the following is considered. Polyester obtained by using terephthalic acid together with the above 2,6-naphthalenedicarboxylic acid, that is, PEN and PET
When a film is prepared using a copolymer or a mixture of the above, the hardness is reduced and the film becomes suitable for photographic use.However, when compared with a homopolymer of PEN, two kinds of carboxylic acids are used. It is considered that it is difficult to form a crystal structure because the polymer chains are difficult to align. Such a low-crystalline polyester film, when heated, because it has a portion that is easily melted, even when applying a coating liquid for forming an undercoat layer on the film and drying,
It is presumed that the heating during the drying causes partial melting and causes wrinkles. According to the study of the present inventors, it has been found that such a polyester film has a large dimensional change at a high temperature, and this dimensional change is a measure of the tendency of wrinkles to occur during drying. The present inventor further studied and found that the film of the present invention having a very small dimensional change at high temperature can be obtained by sufficiently performing heat setting and thermal relaxation after stretching the film.

[0009] The present invention relates to 70-90 mol% ethylene-
It is made of a polyester having a repeating unit composed of 2,6-naphthalate units and 10 to 30 mol% of ethylene terephthalate units, and has a film thickness of 110 to 128 μm.
m is a long polyester film in the range of m
Furthermore, the dimensional change in the width direction and the longitudinal direction at 180 ° C is in the range of -0.6 to 0.6%, and the dimensional change in the width direction and the longitudinal direction at 120 ° C is -0.5 to 0.
A support for a long photographic film, wherein the support is in the range of 5%.

The support of the present invention can be particularly suitably used as a support for a long photographic film having a width of 35 mm or more, such as a 135 type photographic film and a brownie type photographic film. The 135 type photographic film is a film specified in “135 type film / patrone” of JIS K 7519-1982. The 135-type (Leica) photographic film has the dimensions specified above, can be easily filled in the patrone specified above, and is a camera designed for 135-type photographic film as described above. It is required that the film can be used without trouble and that there is no problem in processing operations such as development and fixing of the photographed film. The brownie type photographic film is, for example, JIS K
7512-1994 "120 type and 220 type film". Brownie type photographic film is 120 type (61.5 × 806 mm, with backing paper), 22
Type 0 (61.5 x 1651 mm, type wound around a thin shaft with light-shielding leader paper and trailer paper)
In addition, 620 type, 828 type, 616 type, and 116 type are known. Brownie type photographic film, like 135 type photographic film, can be used without any trouble with a camera designed for brownie type photographic film, and there is no problem in processing operations such as development and fixing of the photographed film. Required.

Preferred embodiments of the support for a long photographic film of the present invention are as follows. 1) The polyester film has two endothermic peaks measured by a differential scanning calorimeter, each having a main peak (usually called a melting point) and a sub-peak having a smaller peak than the main peak within a temperature range of 200 to 300 ° C. Having an endothermic peak, and the secondary peak is 5 to 20 ° C. higher than the temperature of the main peak
It is in the low temperature range. 2) The polyester film is a copolymer composed of ethylene-2,6-naphthalate units and ethylene terephthalate units. 3) The polyester film is polyethylene-2,6-
It is a mixture of naphthalate and polyethylene terephthalate. 4) The loop stiffness of the polyester film is 2
It is in the range of 2 to 55 g (preferably 30 to 50 g). 5) Core set curl value of polyester film is 70
m ^-1 or less (preferably 5 to 70 m ^-1) is. 6) The Young's modulus of the polyester film is 400 to 60.
It is in the range of 0 kg / mm ² . 7) The polyester film is a biaxially stretched film. You. 8) The glass transition temperature of the polyester film obtained from the differential scanning calorimeter is in the range of 103 to 110 ° C. 9) The haze of the polyester film is 2% or less. 10) The polyester film further contains 300 pp of inert fine particles having an average particle size in the range of 0.1 to 1 μm.
m or less. 11) The inert fine particles of the above 10) have a particle size distribution of 0.0
It is in the range of 1-5 μm. 12) The ratio of the area-based fraction of particles having a particle size of 1 μm or more of the inert fine particles of the above item 10) is 20% or less. 13) The inert fine particles of the above 10) are crushed silica. 14) The polyester film is a biaxially stretched film.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The photographic support film of the present invention is a polyester having a repeating unit composed of 70 to 90 mol% of ethylene-2,6-naphthalate unit and 10 to 30 mol% of ethylene terephthalate unit, that is, a polyester. It is made of a polyester having a main repeating unit of ethylene-2,6-naphthalate unit, and shows only a very small dimensional change (rate) or no dimensional change at a high temperature. Such a film can be obtained by subjecting the above polyester to heat treatment and heat relaxation treatment as described later to form a film. The polyester film may be any of a copolymer containing these units, a mixture of homopolymers containing each unit, and a film obtained from a mixture of these polymers.

Examples of the polyester which can be used for producing the polyester film of the present invention include polyethylene-2,6-naphthalate / terephthalate (copolymer having ethylene-2,6-naphthalate unit and ethylene terephthalate unit), PEN And PET. For example, PEN is naphthalene-2,6-
Catalyze dicarboxylic acid or a derivative thereof (an ester-forming derivative such as an anhydride or a lower alkyl ester) and ethylene glycol or a derivative thereof (an ester-forming derivative such as an alkylene oxide) and, if desired, another dihydric alcohol. By reacting (polymerizing) under suitable reaction conditions in the presence of PET is, for example, terephthalic acid or a derivative thereof,
And ethylene glycol or a derivative thereof (a derivative capable of forming an ester such as an alkylene oxide), and if desired, a reaction (polymerization) with another dihydric alcohol in the presence of a catalyst under appropriate reaction conditions. You. The copolymer is, for example, naphthalene-
2,6-dicarboxylic acid or a derivative thereof (an ester-forming derivative such as an anhydride or a lower alkyl ester), terephthalic acid or a derivative thereof, and ethylene glycol or a derivative thereof (an ester-forming derivative such as an alkylene oxide), and further, If desired, it is synthesized by reacting (polymerizing) with another dihydric alcohol in the presence of a catalyst under appropriate reaction conditions. Before the completion of the polymerization of polyethylene-2,6-naphthalate, terephthalic acid or a derivative thereof may be added for copolymerization.

Other dibasic acids other than those mentioned above and benzenedicarboxylic acids or derivatives thereof which can be used in the present invention include isophthalic acid, phthalic acid, sodium isophthalic acid sulfonate (sodium sulfoisophthalic acid) and lower alkyls thereof. Esters (an ester or a derivative capable of forming an ester such as a lower alkyl ester) can be mentioned. Further, as other dicarboxylic acids other than the benzenedicarboxylic acid or derivatives thereof, 2,7-
Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, and lower alkyl esters thereof (an ester-forming derivative such as anhydride and lower alkyl ester); cyclopropanedicarboxylic acid , Alicyclic dicarboxylic acids such as cyclobutanedicarboxylic acid and hexahydroterephthalic acid and derivatives thereof (ester-formable derivatives such as anhydrides and lower alkyl esters); and adipic acid, succinic acid, oxalic acid, azelaic acid, sebacic acid And aliphatic dicarboxylic acids such as dimer acid and derivatives thereof (an ester-forming derivative such as anhydride and lower alkyl ester). These dibasic acids can be used in amounts up to 10 mol% of the total dibasic acid.

The dihydric alcohols other than ethylene glycol which can be used in the present invention include propylene glycol, trimethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, p -Xylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, ethylene oxide adduct of bisphenol A, p, p'-dihydroxyphenylsulfone, 1,4-bis (β-hydroxyethoxyphenyl) propane, polyalkylene (eg , Ethylene, propylene) glycol and p-phenylenebis (dimethylolcyclohexane). These may be used in an amount of 10 mol% or less of the dihydric alcohol.

The above-mentioned polyester may be obtained by blocking a terminal hydroxyl group and / or a carboxyl group with a monofunctional compound such as benzoic acid, benzoylbenzoic acid, benzyloxybenzoic acid, methoxypolyalkylene glycol, or For example, it may be modified with a very small amount of a trifunctional or tetrafunctional ester-forming compound such as glycerin or pentaerythritol as long as a substantially linear copolymer can be obtained.

In the production of polyester, known catalysts can be used for the transesterification reaction, esterification reaction and polycondensation. Further known heat stabilizers, antioxidants, antistatic agents, lubricants, ultraviolet absorbers, fluorescent brighteners,
Pigments, dyes, light-blocking agents, fillers and the like may be added.
As a catalyst for the transesterification reaction, manganese acetate, cobalt acetate, magnesium acetate, calcium acetate, cadmium acetate, zinc acetate, lead acetate, magnesium oxide, lead oxide and the like are generally used. These may be used alone or in combination. Although the esterification reaction proceeds without adding a catalyst, the reaction can be efficiently advanced by using the above-mentioned catalyst. The polycondensation reaction catalyst includes antimony trioxide, antimony pentoxide, antimony trifluoride, antimony sulfide, antimony tributyrate, antimony ethylene glycolate, potassium antimonate, antimony acetate, antimony trichloride, germanium dioxide, germanium dioxide, Germanium oxide, manganese acetate,
Zinc acetate, lead acetate, alkali metal benzoate, titanium alkoxide (eg, titanium butoxide), and alkali metal titanate are generally used. These may be used alone or in combination.

As a heat stabilizer, phosphoric acid, phosphorous acid or ester compounds thereof may be added. Examples thereof include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triphenyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and mono- or diesters of phosphoric acid or phosphorous acid. Further, known hindered phenols may be added as an antioxidant. For example, commercially available products such as Irganox 1010, Sumilizer BHT, and Sumilizer GA-80 can be used. It is also possible to combine a secondary antioxidant with these primary antioxidants. As the secondary antioxidant, for example, those commercially available under the trade names such as Sumilizer TPL-R, Sumilizer TPM, and Sumilizer TP-D can be used.

The above polyester can be obtained by subjecting a dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid or dimethyl 2,6-naphthalenedicarboxylate or a derivative thereof and a dihydric alcohol such as ethylene glycol to a transesterification reaction or an esterification reaction (esterification). (Reaction tank) to obtain an oligomer, and then a polycondensation reaction (polycondensation reaction tank) can be performed under vacuum to synthesize. That is, in the transesterification reaction, 1 to 2 kg of a polybasic acid and a polyhydric alcohol are used.
/ cm ² under pressure or under atmospheric pressure, 180 to 280 ° C.
(Preferably at 230 to 270 ° C.) for 0.5 to 8 hours (preferably 2 to 4 hours) to complete the distillation of the alcohol. The esterification reaction is similarly performed by terminating the outflow of water. Next, the pressure in the tank was reduced to 50 to 1 mmHg, and the pressure was changed to 240 to 2 mmHg.
The temperature is raised to 90 ° C., and if necessary, a high vacuum of 1 mmHg or less is applied, followed by heating for a total of 1 to 3 hours to obtain a polyester.

The polyester film of the present invention contains 300 ppm or less (preferably 50 to 3) of inert fine particles having an average particle diameter of 0.1 to 1.0 μm as a surface slipperiness imparting agent.
(00 ppm). Examples of the inert fine particles include inorganic compounds insoluble in polyester such as talc, silica, aluminum oxide, and calcium carbonate, and organic compounds such as cross-linked polymers such as cross-linked acrylic resin and benzoguanamine resin. Among these, silica is preferred, and crushed silica is particularly preferred. The particle size distribution of the inert fine particles is preferably in the range of 0.01 to 5 μm, particularly preferably in the range of 0.01 to 3 μm. Coarse particles having an average particle diameter of more than 5 μm tend to lower the smoothness of the film surface or generate voids during film formation to increase the haze. Also,
Particles having a particle size of less than 0.01 μm have almost no effect of improving the slipperiness. Furthermore, it is preferable that the area-based fraction of the particles exceeding 1.0 μm of the inert fine particles (preferably crushed silica particles) is 20% or less of all the particles. The expression that the area-based fraction is 20% or less of all the particles means that particles having a size of 1 µm or more are 20% or less in a cumulative distribution curve represented by the area. Particles having an average particle diameter of 1 μm or more
Since voids are easily generated, it is preferable to use inert fine particles having an area-based fraction of particles of 1 μm or more and 20% or less of all particles as described above. Further, the pore volume of the crushed silica particles is preferably 0.1 mL / g or less, and particularly preferably in the range of 0.01 to 0.05 mL / g. Its specific surface area is 10 to 30 m ² / g
Is preferably within the range.

In the present invention, in the polyester film,
In the polyester polymerization step, particles (so-called internal particles) precipitated by reacting a metal compound and a phosphorus compound as a metal phosphate may be included.

As described above, the polyester film of the present invention has physical properties suitable for use as a support for a long photographic film having a width of 35 mm or more. This film is obtained by subjecting a polyester having a repeating unit composed of 70 to 90 mol% of an ethylene-2,6-naphthalate unit and 10 to 30 mol% of an ethylene terephthalate unit to optimum stretching conditions and heat treatment conditions (described below). (Sufficient heat fixation and heat relaxation treatment are performed within the range that does not increase.)
The film is formed by performing a film forming process so that the film thickness is in a range of 110 to 128 μm. The polyester film of the present invention exhibits the following low dimensional changes at high temperatures.
That is, the dimensional change at 180 ° C. in the width direction and the longitudinal direction is −
It is in the range of 0.6 to 0.6%, and the dimensional change at 120 ° C. in the width direction and the longitudinal direction is in the range of −0.5 to 0.5%. Since the dimensional change at the high temperatures of 180 ° C. and 120 ° C. is extremely small, the undercoat layer formed to improve the adhesiveness of the emulsion layer is heated for a long time for drying during its formation, Wrinkles hardly occur on the film surface. In particular, when water is used as the main solvent of the coating liquid for forming the undercoat layer, the use of the support of the present invention is preferable since the drying temperature must be increased. In addition, the said dimensional change can be measured according to the method of measuring the normal heat shrinkage.

Also, the polyester film of the present invention has the following properties:
% Or less (preferably 1% or less). Thereby, the transparency of the film required as a support of the photographic film can be obtained. That is, heat treatment (heating time, temperature) to reduce dimensional change
Is performed in excess, the haze increases. Therefore, in the present invention, it is necessary to manufacture a film in consideration of this point.

Further, the polyester film of the present invention comprises:
As an endothermic peak measured by a differential scanning calorimeter, 2
It has two endothermic peaks in the temperature range of 00 to 300 ° C., which are composed of a main peak (usually called a melting point) and a sub-peak having a smaller peak than the main peak, and the sub-peak is located at a temperature 5 degrees lower than the temperature of the main peak. It is preferably within a temperature range lower by 範 囲 20 ° C. The minor peak may be the shoulder of the peak. Polyesters obtained using terephthalic acid with 2,6-naphthalenedicarboxylic acid, ie PEN and PE
When a film is produced using a copolymer or mixture of T, the hardness is reduced and the film becomes suitable for photographic use. However, two types of carboxylic acids are used when compared with a homopolymer of PEN. Therefore, it is difficult to form a crystal structure because the polymer chains are difficult to align. Such a low-crystalline polyester film is partially melted easily when heated, so that when a coating liquid for forming an undercoat layer is applied to the film and dried, wrinkles due to heating during the drying are obtained. It is thought to occur. When a film is formed by appropriately setting the heat setting temperature and the required time, the heat relaxation temperature and the required time, and the heat relaxation rate according to the polymer composition so that the heat setting and the heat relaxation treatment can be sufficiently performed. In many cases, a small endothermic peak (sub-peak) appearing immediately before the melting point or a shoulder of the endothermic peak is in a temperature range of 5 to 20 ° C. lower than the melting point. That is, when the endothermic peak is lower than this temperature range, it is presumed that a part of the polymer is melted at the heating temperature of the undercoat layer to cause a dimensional change of the film, which is one of the causes of wrinkles.

The polyester film of the present invention preferably further has the following physical properties. Loop stiffness polyethylene-2,6-naphthalate (PEN) in the range of 22 to 55 g is hard to form a curl and shows a low core set curl value, but is suitable for a support for a long photographic film having a width of 35 mm or more. When the film thickness is 110 to 128 μm, the rigidity (stiffness) of the film is large (that is, the loop stiffness is large). For this reason, when a photographic film using such a film as a support is loaded in a camera, troubles often occur when the film is automatically loaded or wound on the camera. Furthermore, due to the high rigidity of the film, problems such as generation of scratches and jamming during transport may occur in, for example, development unevenness during development, or a printing process for forming an image on photographic paper after development. is there. Loop stiffness is greatly affected by the constituent units of the polyester, but with the specific structure of the present invention, by creating a film under optimal film forming conditions,
It can have an appropriate range of values. The loop stiffness is preferably in the range of 30 to 50 g.

Core set curl value of 70 m ^-1 or less The core set curl value indicates the degree of curl tendency. Core set curl values are generally
Polyester having a large amount of 2,6-naphthalate units is good because it has a low value, but on the other hand, the loop stiffness is high, and the above-mentioned problem of automatic loading and automatic winding of a film on a camera cannot be solved. the same as,
It is determined by the composition of the polyester and the forming conditions. The core set curl value is 5 to 70 m in ANSI curl value.
It is preferably in the range of ^-1 . If the longitudinal and transverse direction Young's modulus Young's modulus of 400~600kg / mm ² exceeds 600 kg / mm ^2, the film is too strong, jamming occurs in the camera. Glass transition temperature of 100 ° C. or higher (obtained from a differential scanning calorimeter) A photographic film is sometimes left in a car in the middle of summer, and heat resistance is also required. It is at least necessary to have the above Tg. Glass transition temperature is 103 ~
It is preferably in the range of 110 ° C.

The polyester film of the present invention is produced using a polyester copolymer or a mixture having the above specific composition. The polyester film of the present invention,
It is preferably a biaxially oriented polyester film (biaxially stretched polyester film). Biaxial stretching is generally performed by a tenter type stretching machine. 70-90 mol% of ethylene-2,6-naphthalate units and 10
A polyester having a repeating unit consisting of ３０30 mol% of ethylene terephthalate units, for example, a polyester copolymer having the above composition containing the fine particles or a polyester mixture mixed so as to have the above composition is dried in advance at 280 ° C. After being melt-extruded into a sheet at 330 ° C, it is cooled and solidified at 30 to 110 ° C to produce an amorphous sheet. Then, at 100 ° C. to 160 ° C. (110
C. to 150.degree. C., particularly preferably 120.degree. C. to 135.degree. C.).
Times (preferably 2.5-4 times), then 11
0 to 160 ° C (110 ° C to 150 ° C is preferable;
After stretching in the transverse direction (width direction) 2 to 5 times (preferably 2.8 to 4.5 times) at a temperature of 30 ° C. to 150 ° C.), heat fixation and thermal relaxation are performed as described below. By doing so, a biaxially stretched polyester can be obtained.

That is, heat setting is performed by melting the polyester (corresponding to the main peak of the above-mentioned endothermic peak; PEN / PET = 8 /
(At about 250 ° C. in 2 (molar ratio)) 2 to 15 ° C., after the film reaches that temperature, it is preferable to hold for 3 to 20 seconds, and particularly preferable to hold for 4 to 15 seconds. The thermal relaxation after heat setting is preferably performed at a temperature 5 to 20 ° C. lower than the melting point of the polyester, and held for 3 to 20 seconds after the film reaches the temperature, and particularly preferably 4 to 1 second.
It is preferable to hold for 5 seconds. The relaxation rate at the time of heat relaxation (or at the time of heat fixation) is preferably in the range of 2 to 8%, particularly 3%.
It is preferably in the range of 7%. The thermal relaxation rate can be obtained by reducing the shrinkage by reducing the width of the tenters on both sides during thermal relaxation. Further, the obtained film is preferably subjected to an annealing treatment described below at a temperature equal to or lower than the glass transition temperature of the polyester.

The polyester film having specific properties of the present invention can be obtained by biaxially stretching a polyester copolymer or a mixture having the above specific composition as described above. The film is generally produced by changing the above stretching conditions depending on the composition of the polyester so as to have physical properties. For example, when the polyester is a copolymer (or a mixture of 80 mol% of ethylene-2,6-naphthalate units and 20 mol% of ethylene benzene dicarboxylate units; melting point is about 250 ° C.), longitudinal stretching is performed at 120 ° C. The pre- and post-temperatures are performed at a draw ratio of about 3.5 times, and the transverse draw is 135.
Heating is performed at a temperature of about 40 ° C. and a draw ratio of about 4.0 times, and heat setting is performed at about 235 to 245 ° C. for about 5 to 8 seconds (the number of seconds since the film reaches the heat setting temperature). Thermal relaxation of about 235 to 242 ° C.
(A temperature as low as about ° C) for about 4 to 6 seconds, and it is particularly preferable that the heat relaxation rate is about 3 to 7%.
The polyester film thus obtained can exhibit the above-mentioned specific low heat shrinkage and low haze. If the heat setting and the thermal relaxation are too short, the above-mentioned low heat shrinkage cannot be obtained, while if too long, the haze increases.

The above-mentioned polyester film has significantly improved curl characteristics (the degree of curl after being left in a rolled state), and is hard to be curled. Therefore, the film is not broken at the time of the developing process, and the film is not torn from the perforated portion of the film at the time of winding the film after the film is loaded into the camera.

In the present invention, the biaxially stretched film may be subjected to an annealing treatment (heat treatment) at a temperature in the range of 50 ° C. or more and the glass transition temperature or less after the biaxial stretching and before the application of the emulsion. The time required for performing the annealing treatment is 0.
1-1500 hours are typical. This effect progresses faster as the heat treatment temperature is higher. However, when the heat treatment temperature exceeds the glass transition temperature, the molecules in the film move rather randomly and the free volume increases, and the film easily flows, that is, the film is easily curled. Therefore, this annealing treatment needs to be performed at a temperature lower than the glass transition temperature.

Elongated photographic film using the above polyester film (in general, elongate photographic film having a width of 35 mm or more, such as 135-type or Brownie-type photographic film)
When the polyester film is prepared, since the polyester film has a hydrophobic surface, a photographic layer (for example, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, etc.) composed of a protective colloid mainly composed of gelatin is firmly formed on the support. It is very difficult to adhere to. Prior art attempts to overcome such difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment. , A mixed acid treatment, an ozone oxidation treatment, etc., followed by a method of applying a photographic emulsion directly after applying a surface activation treatment, or a method of applying an undercoat layer after obtaining an adhesive force and coating a photographic emulsion layer thereon. There are two methods: (2) a method of providing an undercoat layer without these surface treatments and coating a photographic emulsion layer thereon.

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

Various modifications have been made to the structure of the undercoat layer. A layer (hereinafter, abbreviated as the first undercoat layer) that adheres well to the support is provided as the first layer, and the second layer is formed thereon. A hydrophilic resin layer that adheres well to the photographic layer
Abbreviated as a layer) and a single-layer method in which only one resin layer containing both a hydrophobic group and a hydrophilic group is applied. (2) The undercoating method is the first undercoating method in the multilayer method.
In the layer, for example, vinyl chloride, vinylidene chloride, butadiene, styrene, methacrylic acid, acrylic acid, itaconic acid, copolymers starting from monomers selected from maleic anhydride and the like, various, Polymers can be used. For example, mention may be made of latex polymers such as styrene / butadiene copolymer, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer, acrylate-containing copolymer, vinyl acetate-containing copolymer, butadiene-containing copolymer. And a styrene / butadiene copolymer is preferred. Along with such polymers,
It is preferable to use a triazine-based crosslinking agent such as 2,4-dichloro-6-hydroxy-s-triazine. Gelatin is mainly used for the second layer of the undercoat.

In the single-layer method, good adhesion is often achieved by swelling a large number of supports and interfacially mixing with a hydrophilic undercoat polymer. Examples of the hydrophilic undercoat polymer used in the present invention include a water-soluble polymer, a cellulose ester, a latex polymer, and a water-soluble polyester. 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.
Examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylate-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. The polyester film of the present invention (support)
Is one in which when the above-mentioned coating liquid for forming an undercoat layer is applied and dried, wrinkles hardly occur due to heating during drying. In particular, when a coating liquid for forming an undercoat layer using a large amount of water as a solvent (or a dispersion medium) is applied to a support and dried, and when two such undercoat layers are formed, drying is performed. Although the temperature is high (and the time is long), wrinkles are likely to occur, but by using the polyester film of the present invention, the undercoat layer can be formed without wrinkles. Therefore, water-soluble resins such as gelatin,
When latex is used in a coating liquid for forming an undercoat layer, the present invention can be said to be effective because it becomes a general main component.

The binder of the back layer may be a hydrophobic polymer or a hydrophilic polymer as used for the undercoat layer. The back layer can contain an antistatic agent, a lubricant, a matting agent, a surfactant, a dye, and the like.
The most preferred antistatic agents are ZnO, TiO.
₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , M
Fine particles of at least one crystalline metal oxide selected from gO, BaO, and MoO ₃ V ₂ O ₅ or composite oxides thereof.

Next, the photographic layer (silver halide emulsion layer) of the long photographic film 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 may contain a coupler, a DIR compound, or the like, and may contain a color mixing inhibitor as usually used.

The silver halide grains include those having regular crystals such as cubic, octahedral, and tetradecahedrons, those having irregular crystal forms such as spheres and plates, and those having twin planes. It may have a crystal defect or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Also, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such a process are described in Research Disclosure Nos. 17643 and 18716.

Various color couplers can be used in the photographic layer, and specific examples thereof are described in Research Disclosure (RD) No. 17643, VII-C to GI, supra.
The patent is described in US Pat.

The light-sensitive material the total thickness of all hydrophilic colloid layers on the side having emulsion layers is not more than 28 .mu.m, and the film swelling speed T _^1/2 is preferably not more than 30 seconds. The film thickness is 25
℃ means a film thickness measured at a relative humidity of 55% (2 days), the film swelling rate T _^1/2 can be measured in accordance with a known method in the art. For example, A. Green et al.
Science and Engineering (Photog
r. Sci. Eng. ), Vol. 19, No. 2, 124-12
Can be measured by using a type of Swellometer described (swelling meter) pages 9, T _^1/2 is 30 ° C. in a color developing solution, 3
90% of the maximum swollen film thickness reached when treated min 15 seconds and the saturated film thickness, which time defined to reach the thickness of the T ^_1/2.

The diameter of the cartridge spool for loading the 135-type film is usually 10 to 14 mm, especially 11 to 13 mm. Further, in the case of a brownie type film, 11 to 13 mm is generally used for 120 type and 220 type.

[0042]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, "parts" means parts by weight.

[Synthesis Example 1] (Production of polyethylene-2,6-naphthalate) In a transesterification reactor, 100 parts of dimethyl 2,6-naphthalenedicarboxylate, 58 parts of ethylene glycol, and 0.029 part of manganese acetate tetrahydrate were placed. And antimony trioxide 0.02
After charging 8 parts, the contents were heated to 200 ° C. while stirring. Next, the temperature in the system was raised to 235 ° C. while removing methanol produced as a by-product from the reaction from the rectification column. After confirming that the by-product of methanol has ended,
The reaction product was transferred to a polycondensation tank and trimethyl phosphoric acid 0.0
30 parts were added. While the content was heated to 285 ° C., the pressure inside the tank was gradually reduced, and finally the pressure was reduced to a vacuum of 0.3 Torr. In this state, a polycondensation reaction is carried out for about 2 hours, and crushed silica having an intrinsic viscosity of 0.58 (average particle diameter:
0.5 μm) and polyethylene-2,6 containing 150 ppm.
-Naphthalate was obtained.

[Synthesis Example 2] (Production of polyethylene terephthalate)
Polyethylene terephthalate containing silica particles was obtained in the same manner as in Synthesis Example 1, except that 80 parts of dimethyl terephthalate was used instead of 100 parts of dimethyl 2,6-naphthalenedicarboxylate. The intrinsic viscosity of the obtained polyester was 0.65.

[Synthesis Example 3] (Production of polyethylene 2,6-naphthalate / terephthalate (copolyester))
Same as Synthesis Example 1 except that 83.3 parts (80 mol%) of 2,6-naphthalenedicarboxylic acid dimethyl and 16.7 parts (20 mol%) of dimethyl terephthalate were used instead of 100 parts of dimethyl naphthalenedicarboxylate Polyethylene-2,6-naphthalate containing silica particles
Terephthalate (copolymerized polyester) was obtained. The intrinsic viscosity of the obtained polyester is 0.59, and the melting point is 250 ° C.
Met.

Example 1 A pellet of polyethylene-2,6-naphthalate / terephthalate (molar ratio of naphthalate / terephthalate 80/20) obtained in Synthesis Example 3 was dried at 100 ° C. under reduced pressure for 12 hours. The dried pellets were fed from a hopper into an extruder equipped with a 10 μm mesh filter. The polyester was melt-mixed in a heated extruder for 4 minutes (residence time), and the molten polyester heated to 300 ° C. was passed through a T die to a surface temperature of 50 ° C.
It was melt-extruded into a sheet on a casting drum at a temperature of 150 ° C. to obtain an amorphous sheet having a thickness of 1.5 mm. Next, the amorphous sheet is stretched 3.6 times in the longitudinal direction (long-length direction) at a temperature of 120 ° C., and then cooled.
After stretching 4.0 times in the transverse direction (width direction) at a temperature of ° C., heat-fixed at 240 ° C. for 8 seconds, and then thermally relaxed at 235 ° C. for 6 seconds at a relaxation rate of 3% in the width direction. After cooling, a biaxially stretched film having a thickness of 120 μm was produced. Biaxial stretching was performed using a tenter type stretching machine.

[Examples 2 to 6] The procedure of Example 1 was repeated except that the longitudinal stretching conditions, the transverse stretching conditions, the heat setting conditions, and the thermal relaxation conditions were changed as shown in Table 1. A biaxially stretched polyester film having the thickness shown in Table 1 was obtained in the same manner as in Example 1.

Example 7 The PEN pellets obtained in Synthesis Example 1 and the PET pellets obtained in Synthesis Example 2 were prepared by mixing ethylene-2,6-naphthalate units and ethylene terephthalate units with 90 mol% and 10 mol%, respectively. And dried at 100 ° C. under reduced pressure for 12 hours. The dried pellet mixture was fed from a hopper into an extruder equipped with a 10 μm mesh filter. Melt mixing the polyester in a heated extruder for 4 minutes (residence time),
The molten polyester heated to 300 ° C. was melt-extruded from a T-die into a sheet on a casting drum having a surface temperature of 50 ° C. to obtain an amorphous sheet (melting point: 260 ° C.) having a thickness of 1.5 mm. Next, the amorphous sheet is
The film was stretched 3.6 times in the longitudinal direction (long direction) at a temperature of 25 ° C., cooled, and then stretched 4.0 times in the transverse direction (width direction) at a temperature of 140 ° C. The film was heat-set at 16 ° C. for 16 seconds, then thermally relaxed at 245 ° C. for 12 seconds at a relaxation rate of 5% in the width direction, and cooled to produce a biaxially stretched film having a thickness of 120 μm. Biaxial stretching was performed using a tenter type stretching machine.

Example 8 The PEN pellets obtained in Synthesis Example 1 and the PET pellets obtained in Synthesis Example 2 were prepared by mixing ethylene-2,6-naphthalate unit and ethylene terephthalate unit in 75 mol% and 25 mol%, respectively. And dried at 160 ° C. under reduced pressure for 19 hours. The dried pellet mixture was melt-extruded in the same manner as in Example 7 to obtain an amorphous sheet (melting point: 245 ° C.). Next, the amorphous sheet is placed in a longitudinal direction (long direction) at a temperature of 117 ° C.
Stretched 3.6 times, then cooled, stretched 4.0 times in the transverse direction (width direction) at a temperature of 133 ° C.,
Heat set at 5 ° C. for 5 seconds, then relax at 230 ° C. for 4 seconds in the width direction at a relaxation rate of 5%, cool to 125 μm in thickness
m was prepared. Biaxial stretching was performed using a tenter type stretching machine.

[Comparative Examples 1 to 5] The procedure was performed in the same manner as in Example 1 except that the longitudinal stretching conditions, the transverse stretching conditions, the heat setting conditions, and the thermal relaxation conditions were changed as shown in Table 1. A biaxially stretched polyester film having the thickness shown in Table 1 was obtained in the same manner as in Example 1.

The conditions for producing the biaxially stretched film are shown in Table 1 below.

[0052]

[Table 1] Table 1 ──────────────────────────────────── Film Longitudinal stretching Lateral stretching Heat setting Heat Relaxation Resin composition Thickness Magnification / Magnification / Temperature / sec. Temperature / sec. / Rate (EN / ET (mol%)) (μm) Temperature (° C) Temperature (° C) (° C) (° C) (%) ──── ──────────────────────────────── Example 1 80/20 copolymer 120 3.6 / 120 4.0 / 135 240/8 235 / 6/3 Example 2 80/20 copolymer 120 3.6 / 120 4.0 / 135 240/8 235 / 6/5 Example 3 80/20 copolymer 120 3.6 / 120 4.0 / 135 240/8 235/6 / 7 Example 4 80/20 copolymer 115 3.5 / 120 4.1 / 135 235/5 235 / 4/5 Example 5 80/20 copolymer 118 3.6 / 120 4.0 / 135 245/5 235/4/4/5 Example 6 80/20 copolymer 120 3.6 / 120 4.0 / 135 240/5 242 / 4/5 Example 7 90/10 mixing 120 3.6 / 125 4.0 / 140 247/16 245 / 12/5 Example 8 75/25 mixing 125 3.6 / 117 4.0 / 135 235/5 230/4/5 ─────────比較 Comparative Example 1 80/20 copolymer 120 3.6 / 120 4.0 / 135 240/2 235/2/5 Example 2 80/20 copolymer 120 3.6 / 120 4.0 / 135 230/8 230 / 6/5 Comparative Example 3 80/20 copolymer 120 3.6 / 120 4.0 / 135 230/8 225 / 6/5 Comparative Example 4 80 / 20 Copolymer 118 3.6 / 120 4.0 / 135 240/8 235 / 6/9 Comparative Example 5 80/20 Copolymer 120 3.6 / 120 4.0 / 135 240/8 235 / 6/1 Comparative Example 6 80/20 Copolymer 115 3.6 / 120 4.0 / 135 240/22 235/22/5 ──────────────────────────────────── In addition, as for the temperature under the heat fixing condition and the thermal relaxation condition, the temperature of the film surface was measured with a radiation thermometer.

The biaxially stretched film obtained above was further annealed at 95 ° C. for 24 hours, and then evaluated for characteristics. The polyester or biaxially stretched film obtained above was measured and evaluated according to the following measurement method. (1) Endothermic main peak (melting point (Tm)) Obtained polyester or unstretched sheet (mixture) 50
mg was measured using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation) at a heating rate of 10 ° C./min in a nitrogen stream. Obtain a DSC thermogram. The temperature (corresponding to Tm in FIG. 1) at which the maximum endothermic peak was found within the range of 200 to 300 ° C. in the DSC thermogram. (2) Endothermic sub-peak (temperature of melting point pre-peak) Using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation), 50 mg of the obtained biaxially stretched polyester film was heated at a rate of 10 ° C./min under a nitrogen stream. Measured at temperature rate. FIG.
A DSC thermogram as shown in (obtained in Example 2) is obtained. In the DSC thermogram, 2
A temperature (Tp in FIG. 1) showing an endothermic peak (the above-mentioned melting point prepeak) in a temperature range lower than the temperature showing the maximum endothermic peak (Tm in FIG. 1) in the range of 00 to 300 ° C. is obtained. (3) Dimensional change The obtained biaxially stretched polyester film is longitudinally (longitudinally).
1.5cm in the direction and 20cm in the width direction.
The obtained sample was placed in an air thermostat set at 180 ° C. and an air thermostat set at 120 ° C., left for 3 minutes, and then taken out. Vertical direction (MD), width direction (T
For each of D), the length before putting in a thermostat,
The dimensional change was calculated from the length taken out of the thermostat by the following formula.

(4) Haze (Transparency) The haze of the polyester film was measured with a haze meter (N
DH-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.). (5) Loop stiffness (rigidity) The obtained polyester film was 10 mm x 180 mm
, And a loop was formed at a portion having a length of 100 mm near the center of the film, and the load applied when the loop was pushed 10 mm from the outside was measured. This measurement was performed using "Loop Stiffness Tester" (manufactured by Toyo Seiki Seisaku-sho, Ltd.). (6) Core set curl value The obtained polyester film was 35 mm x 120 mm
And wrap it around a 11.5 mm diameter core.
After leaving in an atmosphere of 0 ° C. for 2 hours, the film was removed from the core. Curl value (curl habit) of the obtained film
Was measured. The curl value was represented by 1 / R [m ^-1 ] (R is the radius of the curl).

Table 2 shows the results obtained above.

[0056]

[Table 2] Table 2 ──────────────────────────────────── EN / ET Main Pi Secondary Pi 180 ℃ 120 ℃ haze loop car mark Dimensional change Dimensional change Still value MD TD MD TD Funes (mol%) (° C) (° C) (%) (%) (%) (%) (%) (g) (m ^-1 ) ──────────────────────────────────── Example 1 80/20 250 238 0.2 0.6 0.1 0.3 0.2 39 35 Example 2 80/20 250 237 0.4 0.4 0.1 0.2 0.2 40 34 Example 3 80/20 250 237 0.3 0.1 0.2 0.2 0.3 39 37 Example 4 80/20 250 232 -0.4 0.6 0.6 0.4 0.2 35 36 Example 5 80/20 250 242 0.1 0.1 -0.3 -0.1 0.3 42 35 Example 6 80/20 250 237 -0.1 -0.1 -0.3 -0.2 0.3 35 33 Example 7 90/10 260 246 0.2 -0.1 0.1 -0.2 0.5 46 30 Example 8 75/25 245 230 0.3 -0.5 0.1 -0.5 0.2 32 44 ──────────────────────────── ──────── Comparative Example 1 80/20 250- ^* 1.9 1.5 1.2 1.3 0.2 29 37 Comparative Example 2 80/20 250 228 1.6 0.6 0.9 0.2 0.3 31 36 Comparative Example 3 80/20 250 227 0.7 1.4 0.5 1.0 0.3 32 38 Comparative Example 4 80/20 250 228 0.7 -0.5 0.4 -0.7 0.6 40 35 Comparative Example 5 80/20 250 238 0.4 1.8 0.2 1.3 0.2 38 39 Comparative Example 6 80/20 250 238 0.1 0.1 -0.5 0.1 2.6 52 38 ───── ─────────────────────────────── Remarks) ^{* No} peak was detected.

As is clear from Table 1, in Comparative Examples 1 to 3 in which the temperature and time for heat setting and thermal relaxation are not sufficient, the dimensional change is large and the thermal relaxation is too large. Comparative Example 4 and the thermal relaxation is too small. Example 5 was similar. In Comparative Example 6 in which the time for heat setting and thermal relaxation was too long, the haze increased.

For the evaluations (7) to (11) described later,
An undercoat layer was provided on the obtained polyester film as described below, and an emulsion layer was further provided. After glow discharge treatment was performed on the polyester biaxially stretched film that had been annealed as described above, a first undercoat layer and a second undercoat layer having the following composition were formed on one surface thereof as follows. Next, an antistatic layer and a surface layer were formed in this order on the opposite surface of the film as follows. Next, a photosensitive layer (high-sensitivity photographic emulsion layer) was formed on the second undercoat layer as described below to prepare a photographic film (sensitive material).

The following cloth solution for forming a first undercoat layer was coated on the surface-treated support and dried at 180 ° C. for 30 seconds to form a first undercoat layer having a thickness of 0.3 μm. [Cloth liquid for forming first undercoat layer] Styrene / butadiene copolymer latex 6.3 parts by weight (styrene: butadiene = 67: 30 (molar ratio), solid content 40% by weight) 2,4-dichloro-6- Hydroxy-s-triazine 0.2 parts by weight Sodium salt Distilled water 73.5 parts by weight

The following second undercoat layer forming cloth solution was applied on the first undercoat layer, and dried at 170 ° C. for 30 seconds to form a 0.15 μm-thick second undercoat layer. [Clot solution for forming second undercoat layer] Gelatin 1.6 parts by weight Polystyrene fine particles (average particle size: 2 μm) 0.06 parts by weight Compound (1) below 0.006 parts by weight Compound (2) below. 006 parts by weight Glycine 0.05 parts by weight Distilled water 98.278 parts by weight

[0061]

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After the formation of the undercoat layer, an antistatic layer and a surface layer having the following composition were applied on the surface opposite to the side on which the undercoat layer was provided.

[Coating Liquid for Antistatic Layer] Acrylic resin aqueous dispersion (3.1 parts by weight of (meth) acrylic acid ester copolymer); Julimer ET410 (water dispersion, solid content 20% by weight, Nippon Pure Chemical Co., Ltd. 16.5 parts by weight of tin oxide-antimony oxide dispersion (average particle size: 0.1 μm; 30% by weight) 0.1 parts by weight of polyoxyethylene phenyl ether 0.2 parts by weight of melamine compound (Sumitex) Resin M-3 (water-soluble melamine compound, active ingredient concentration: 80% by weight, manufactured by Sumitomo Chemical Co., Ltd.) Distilled water was added to prepare a total of 100 parts by weight. The polyethylene terephthalate film was coated on the surface on which no undercoat layer was provided, and dried at 180 ° C. for 30 seconds to form an antistatic layer having a thickness of 0.03 μm.

[Coating Liquid for Surface Layer] Polyolefin 3.0 parts by weight (Chemipearl S-120, 27% by weight, manufactured by Mitsui Petrochemical Co., Ltd.) Colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) 0 parts by weight Epoxy compound 0.3 parts by weight (Denacol EX-614B; manufactured by Nagase Kasei Co., Ltd.) 0.1 parts by weight of polyethylene sulfonate (molecular weight: 1000 to 5000) 9 parts by weight of distilled water 94.6 parts by weight A liquid is applied on the antistatic layer,
After drying at 70 ° C. for 30 seconds, a surface layer having a layer thickness of 0.03 μm was formed.

Coating of photosensitive layer On the second undercoat layer of the support obtained by the above-mentioned method, layers having the following compositions were applied in multiple layers to prepare a multilayer color photosensitive material. [Composition of photosensitive layer] The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye

The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

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-33 0.1 × 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 0.010 Gelatin 0.75

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

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

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

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

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

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

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

Twelfth Layer (Medium Speed Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-30 .10 HBS-1 0.050 gelatin 0.78

Layer 13 (High-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0 .86

14th layer (first protective layer) Emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00

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

Further, 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 compounds and iron salts, lead salts, gold salts,
Contains platinum, iridium and rhodium salts.
Table 3 shows the composition of the emulsion used for each layer.

[0083]

[Table 3]

In Table 3, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples in JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. It has been subjected. (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.

Next, the chemical formulas and the like of the compounds used for each layer are shown.

[0086]

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[0087]

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[0088]

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[0089]

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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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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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The obtained photographic film (sensitive material) was subjected to JIS
The film is cut to a size satisfying KK7519-1982 and wound around a winding core (11.5 mm) to produce a roll film of 35 mm, and this film is JIS KK7519-198.
2 was loaded into a patrone having dimensions that satisfied it. The following tests were performed using the patrone loaded with this photographic film.

(7) Surface condition at the time of forming an undercoat layer A coating solution for forming an undercoat layer is applied to the surface of the obtained photographic film, and the surface condition is observed when the undercoat layer is formed by heating and drying. And evaluated as follows. AA: No wrinkles generated BB: Slight wrinkles generated, but no wrinkles were selected and used as a photographic support CC: Wrinkles were generated and could not be used as a photographic support (8) Development Using a patrone loaded with the obtained photographic film, the loaded photographic film was developed by an automatic developing machine. The presence or absence of development spots due to development unevenness observed after the development processing was observed. AA: No development unevenness BB: There is development unevenness (9) Fogging The obtained photographic film was left in an environment of a temperature of 75 ° C. and a humidity of 80% for 96 hours, developed without being exposed, and evaluated as follows. . AA: No fog was observed. BB: Fog was slightly observed. CC: Many fogs were observed. (10) Generation of Out-of-focus A patrone loaded with the obtained photographic film was loaded into a camera, actual photographing was performed, and after development, the negative film was observed to check for out-of-focus. AA: No out-of-focus occurred. BB: Out-of-focus occurred. (11) Handling after Loading in Camera A patrone loaded with the obtained photographic film was loaded in a camera, and automatic loading and automatic winding were performed. During these operations, the occurrence of jamming (clogging) was observed. AA: No jamming occurred BB: Jamming occurred CC: Jamming occurred significantly

Table 4 shows the results obtained above.

[0107]

[Table 4] ──────────────────────────────────── Developing spots on film undercoat Out-of-focus handling Resin composition Surface condition (jamming) (EN / ET (mol%)) ──────────────────────────────── ──── Example 1 80/20 AA AA AA AA AA Example 2 80/20 AA AA AA AA AA Example 3 80/20 AA AA AA AA AA Example 4 80/20 AA AA AA AA AA Example 5 80/20 AA AA AA AA Example 6 80/20 AA AA AA AA AA Example 7 90/10 AA AA AA AA AA Example 8 75/25 AA AA AA AA ──────────────────────────── Comparative Example 1 80/20 CC AA AA AA AA Comparative Example 2 80/20 C CAAAAAAAAA Comparative Example 3 80/20 CCAAAAAAAAAA Comparative Example 4 80/20 BBAAAAAAAA Comparative Example 5 80/20 BBAAAAAAAAAA Comparative Example6 80/20 AA ^* ---- −− −− ──────────────────────────────────── ^* However, low transparency and support for photography Cannot be used as a body.

[0108]

The support for a photographic film according to the present invention comprises 13
Formation of an undercoat layer provided to improve the adhesiveness between the photographic emulsion layer and the support, in addition to the properties required for a roll-shaped film such as a type 5 or brownie film, such as being difficult to roll up. Occasionally, it has the property that wrinkles and irregularities do not occur on the surface of the support due to heating for its formation, so that it has the advantage that a photographic film can be produced without any trouble. This problem of wrinkling is particularly likely to occur when the solvent of the coating liquid for forming an undercoat layer contains water as a main component and the drying temperature needs to be raised.
The 135 type or brownie type photographic film using the polyester film of the present invention as a support has no problem in handling after loading the camera, and does not cause spots after development and no blurring of the photographic image. further,
Since the photographic film support of the present invention is not formed by using a solvent like a TAC film, it can be produced without concern about air pollution and working environment pollution.

[Brief description of the drawings]

FIG. 1 is a DSC thermogram of a film for a photographic support obtained in Example 2 of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takanori Sato 200, Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd.

Claims (5)

[Claims] 1. 70 to 90 mol% of ethylene-2,6-
An elongated polyester film comprising a polyester having a repeating unit comprising a naphthalate unit and 10 to 30 mol% of an ethylene terephthalate unit, and having a film thickness in a range of 110 to 128 μm, further comprising 18
Dimensional change in the width and length directions at 0 ° C. is −0.6
A support for a continuous photographic film, wherein the dimensional change in the width direction and the longitudinal direction at 120 ° C. is in the range of −0.5 to 0.5%. . 2. The polyester film has an endothermic peak measured by a differential scanning calorimeter of 200 to 30.
A temperature range of 0 ° C. having two peaks consisting of a main peak and a sub-peak having a smaller peak than the main peak, and the sub-peak being in a temperature range of 5 to 20 ° C. lower than the temperature of the main peak. Item 2. A long polyester film according to item 1. 3. The method according to claim 1, wherein the polyester film is ethylene-
2. The support according to claim 1, which is a copolymer comprising 2,6-naphthalate units and ethylene terephthalate units. 4. The support according to claim 1, wherein the polyester film is a mixture of polyethylene-2,6-naphthalate and polyethylene terephthalate. 5. The polyester film has a width of 35 m.
The support for a long photographic film according to claim 1, which is a support for a long photographic film having a length of at least m.