JPH10293381A - Support body for long size photographic film and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a support body for a long size photographic film which is composed of polyester using an ethylene-2,6-naphthalate unit as a main repeating unit and is excellent in cutting performance. SOLUTION: In a long size film composed of polyester having a repeating unit composed of an ethylene-2,6-naphthalate unit exceeding 95 mole % and an ethylene benzene dicarboxylate unit less than 5 mole %, width directional tearing strength is also not more than 400 g/mm, and lengthwise directional loop stiffness is not more than 50 g/100 μm.

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.
The present invention relates to a photographic film support which can be used for a long photographic film such as a 35 type or brownie type photographic film and a method for producing the same.

[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, a support for a conventional 135-type or brownie-type film is also used for the polyethylene-based film.
Investigations have been made in the direction of using 2,6-naphthalate (PEN). However, P as a support
A photographic film produced using an EN film is generally too hard, and thus has a problem in handling such as easy occurrence of trouble during automatic loading onto a camera and automatic winding. The present inventor further studied that, in addition to the above-mentioned problems, when the development processing was further performed using a small automatic developing machine (Minilab), the cutting property of the film was inferior to that using a conventional TAC film. It became clear that there were cases where cutting was not possible.

[0005]

SUMMARY OF THE INVENTION The inventor of the present invention has proposed a method of using a PEN film as a support for a 135-type or brownie-type film, that is, to improve the cutting performance in a small automatic processor together with the above-mentioned handling. The present inventors have conducted various studies to arrive at the present invention. An object of the present invention is to provide a support for a long photographic film which is made of a polyester having an ethylene-2,6-naphthalate unit as a main repeating unit and has excellent cuttability. Another object of the present invention is to provide a camera with good handling suitability, excellent cuttability, excellent adhesion with a coating layer (such as an undercoat layer) formed on the surface, and further excellent cleavage. An object of the present invention is to provide a support for a long photographic film (that is, excellent in processability such as cutting and perforation).

[0006]

Means for Solving the Problems A PEN film is generally produced by biaxial stretching, but polymer molecules are arranged in the stretching direction, and the film strength is improved in each direction. However, according to the study of the present inventors, it has been clarified that such an improvement in the film strength is not necessarily limited to properties suitable for a photographic support. That is,
As described above, the 135-type film is developed using a small automatic developing machine, but is cut in the width direction during the development. In this case, it has been clarified that the film stretched sufficiently in the longitudinal direction has a large resistance to the cutting in the width direction, and may not be cut in some cases. The present inventor has conducted studies based on the above findings, and has found that it can be achieved by a PEN film obtained by performing only stretching in the horizontal direction while hardly performing stretching in the vertical direction. In addition, since such a film has a good cleavage property, there is no occurrence of irregularities on the cut surface subjected to the slit processing or the perforation processing, and it shows a good workability, and furthermore, an undercoat layer applied to the support surface. It was also found that the adhesiveness with the adhesive was excellent. Further, the photographic film obtained using such a support also had good handling suitability for the camera as described above.

[0007] The present invention relates to a process for preparing ethylene-
A long film made of a polyester having a repeating unit composed of 2,6-naphthalate units and less than 5 mol% of ethylenebenzenedicarboxylate units, and further having a tear strength in the width direction of 400 g / mm or less, And the loop stiffness in the length direction is 50 g / 1
It is a support for a long photographic film, which is not more than 00 μm.

The long photographic film obtained by forming a silver halide emulsion layer (emulsion layer) on the support of the present invention has a width of 35 mm or more, such as a 135 type photographic film or a brownie type photographic film. Elongated photographic films can be mentioned. 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 × 1651 mm, light-shielding leader paper, with trailer paper, type wound on a fine shaft) is the main type, and types 620, 828, 616, and 116 are also 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 width of the film is 35 mm or more. 2) The thickness of the film is 90 to 130 μm (particularly 10
0 to 128 μm). 3) The polyester is polyethylene-2,6-naphthalate. 4) The ethylene benzene dicarboxylate unit is an ethylene terephthalate unit. 5) Loop stiffness in the length direction is 30 g / 100
μm or less (particularly in the range of 10 to 30 g / 100 μm). 6) The tear strength in the width direction is in the range of 200 to 400 g / mm. 7) The core set curl value is in the range of 20 to 155. 8) The glass transition temperature (obtained from a differential scanning calorimeter) is in the range of 100 to 115 ° C. 9) Haze 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 particle diameter distribution of the inert fine particles of the above 10) is 0.
It is in the range of 01 to 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.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The polyester film which is a support for a continuous photographic film of the present invention has an ethylene-2,6-naphthalate unit having a repeating unit in an amount exceeding 95 mol% (of all repeating units). It is composed of less than 5 mol% of ethylene benzene dicarboxylate units. Preferred ethylene benzene dicarboxylate units include ethylene terephthalate units. The polyester film is made of polyethylene-2,6-naphthalate, ethylene-2,6-
Any of a copolymer comprising a naphthalate unit and an ethylenebenzenedicarboxylate unit and a film obtained from a mixture of a homopolymer containing each unit may be used.

The polyester used for preparing the polyester film of the present invention is, for example, naphthalene-2,6
-A dicarboxylic acid or a derivative thereof (an ester-forming derivative such as an anhydride or a lower alkyl ester), if necessary, a benzenedicarboxylic acid or a derivative thereof, and ethylene glycol or a derivative thereof (an ester-forming derivative such as an alkylene oxide); If desired, it is synthesized by reacting (polymerizing) with another dihydric alcohol in the presence of a catalyst under appropriate reaction conditions. The polyester may be a copolymer obtained by adding benzenedicarboxylic acid or a derivative thereof before the completion of the polymerization of polyethylene-2,6-naphthalate.

[0012] Benzenedicarboxylic acid or a derivative thereof includes terephthalic acid, isophthalic acid, phthalic acid, sodium isophthalic acid sulfonate (sodium sulfoisophthalic acid) and lower alkyl esters thereof (anhydrides, lower alkyl esters and the like). Derivative) can be used. Terephthalic acid and sodium isophthalic acid sulfonate are preferred, especially terephthalic acid. Other dihydric alcohols other than ethylene glycol that 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, p, p'-dihydroxyphenylsulfone,
Examples thereof include 1,4-bis (β-hydroxyethoxyphenyl) propane, polyalkylene (eg, ethylene, propylene) glycol, and p-phenylenebis (dimethylolcyclohexane). These may be used in amounts less than 5 mol% of the dihydric alcohol.

The above-mentioned polyester may be one in which terminal hydroxyl groups and / or carboxyl groups are blocked 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.

As long as the polyester used for producing the polyester film of the present invention has the above-mentioned composition, even if it is the above-mentioned copolymer, each homopolymer (eg, polyethylene-2, 6-naphthalate, polyethylene benzene dicarboxylate such as polyethylene terephthalate).

Known catalysts can be used for the esterification reaction, transesterification reaction and polycondensation in the production of polyester. 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. Also, polycondensation reaction catalysts include 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 alkoxides (eg, titanium butoxide), and alkali metal salts of titanic acid and the like 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 synthesis of the polyester will be described in detail. For example, 2,6-naphthalenedicarboxylic acid or 2,6
-An oligomer is obtained by subjecting a dicarboxylic acid such as dimethyl naphthalenedicarboxylate or a derivative thereof to a dihydric alcohol such as ethylene glycol by an ester exchange reaction or an esterification reaction (ester reaction tank), and then a polycondensation reaction (polycondensation) under vacuum. (Reaction tank). That is, the transesterification reaction is carried out by subjecting a polybasic acid and a polyhydric alcohol to a pressure of 1 to ² kg / cm ² or an atmospheric pressure at 180 to 280 ° C (preferably 230 to 270 ° C).
For 0.5 to 8 hours (preferably 2 to 4 hours),
This is performed by terminating the distillation of 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 temperature was raised to 240 to 290 ° C.
The polyester is obtained by heating under a high vacuum of not more than Hg for a total of 1 to 3 hours.

The polyester film of the present invention contains 300 ppm or less (preferably 50 to 3) of inert fine particles having an average particle size 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 0.01 to 5 μm.
The range of m is preferable, and the range of 0.01 to 3 μm is particularly preferable. 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. Further, particles having a particle size of less than 0.01 μm have almost no effect of improving the slipperiness.

Further, it is preferable that the area-based fraction of the inert fine particles (preferably crushed silica particles) exceeding 1.0 μm is not more than 20% 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. Since particles having an average particle diameter of 1 μm or more easily generate voids, it is preferable to use inert fine particles having an area-based fraction of 1 μm or more of 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 10-30 m ²
/ G is preferable.

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 properties optimal for a long-sized photographic film support having a width of 35 mm or more, such as a 135-type photographic film and a brownie-type photographic film (handleability to a camera, cutability). Etc.). In order to obtain such properties, a polyester having a specific repeating unit consisting of more than 95 mol% of ethylene-2,6-naphthalate units and less than 5 mol% of ethylene benzene dicarboxylate units is subjected to the following optimum processing conditions: That is, a polyester film is produced by performing a film forming process under the condition that the film is hardly stretched in the vertical direction and stretched in the horizontal (width) direction.

The polyester film of the present invention has a tear strength in the width direction of 400 g / mm or less and a loop stiffness in the length direction of 50 g / 100 μm or less (preferably 30 g / 100 μm or less). Polyethylene-
2,6-naphthalate (PEN) has a low core set curl value when it is subjected to a normal biaxial stretching process and has a low core set curl value when a film is produced. In addition to problems such as the occurrence of troubles, there is a problem that the cutting properties in the width direction are poor and that cutting may not be performed when processing is performed by a small automatic developing machine. The PEN film of the present invention obtained by performing only stretching in the transverse direction with little stretching in the longitudinal direction has a low tear strength in the width direction and a small loop stiffness in the longitudinal direction. It is considered that such a property leads to an improvement in the cutting property in the width direction, and also improves the handling property for the camera. In particular, it is considered that a low tear strength in the width direction leads to an improvement in cuttability in the width direction. Furthermore, such a film has excellent cleavage properties,
Slits and perforations do not have irregularities on the cut surface, show good workability, and have the advantage of excellent adhesion to the undercoat layer applied to the support surface. .

Further, the film of the present invention causes problems such as generation of scratches and jamming at the time of transportation, for example, due to uneven development at the time of development, or a printing step of forming an image on photographic printing paper after development. There is almost no. The lengthwise loop stiffness of the polyester film of the present invention is preferably in the range of 10 to 30 g / 100 μm. Further, the tear strength in the width direction is 200 to 400 g / mm.
Is preferable.

In the polyester film of the present invention,
The thickness of the film is generally in the range of 90 to 130 μm. For use in 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 film thickness is 100 to 130 μm. A range of 128 μm is particularly preferred. The glass transition temperature is 100 to 115.
C is preferable, and the core set curl value (ANSI curl value) is preferably 70 m ^-1 or less (preferably 5 to 70 m ^-1 , particularly 5 to 40 m ^-1 ). Further, the haze of the film is preferably 2% or less. In particular, the core set curl value and the tear resistance are generally improved by the heat treatment (annealing treatment) after the above stretching.

The polyester film of the present invention having the above-mentioned physical properties comprises polyethylene-2,6-naphthalate, or more than 95 mol% of ethylene-2,6-naphthalate units and less than 5 mol% of ethylenebenzenedicarboxylate units. It is prepared using a copolymer or a mixture to be prepared. The polyester film of the present invention,
The polyester film is preferably a uniaxially stretched polyester film in the width direction or a biaxially stretched film stretched in the width direction after being slightly stretched in the length (longitudinal) direction. Stretching in the width direction is generally performed by a tenter type stretching machine.

The biaxially stretched polyester film containing ethylene-2,6-naphthalate unit as a main component is, for example,
Polyethylene-2,6-naphthalate (or polyester copolymer or polyester mixture) containing the particles is dried in advance, melt-extruded into a sheet at 280 to 330 ° C., and then solidified by cooling at 30 to 110 ° C. without stretching. Make a sheet. Next, 100 ° C to 160 ° C
(110 ° C. to 150 ° C. is preferred, and 125 ° C. to 14
At a temperature of 5 ° C. is preferred) in the longitudinal direction (long direction).
It is stretched twice, and then 110-160 ° C (110 ° C-
After stretching in the transverse direction (width direction) 2.5 to 6 times (preferably 2.5 to 4.5 times) at a temperature of preferably 150 ° C., particularly preferably 115 ° C. to 145 ° C., the polyester From a temperature 40 ° C. or more higher than the glass transition temperature (Tg) to the melting point of the polyester (Tm; 200 to 30 by differential thermal analysis)
The biaxially stretched polyester can be obtained by performing heat treatment in a temperature range (generally 165 to 290 ° C. (preferably 165 to 250 ° C.)) up to 10 ° C. or lower than the temperature of the endothermic peak appearing in the range of 0 ° C.). it can. After the heat treatment, the heat relaxation treatment may be performed at a temperature lower by about 5 ° C. than the heat treatment temperature. During thermal relaxation, shrinkage can be reduced by reducing the tenter width on both sides. The shrinkage rate during the heat relaxation treatment is preferably about 3 to 8%. Further, the obtained film may be subjected to an annealing treatment at a temperature equal to or lower than the glass transition temperature of the polyester.

The polyester film of the present invention may be a film uniaxially stretched in the width direction. This uniaxially stretched film in the width direction can be obtained by directly performing the above-mentioned transverse stretching process on a non-stretched sheet.

In the present invention, the stretched film may be subjected to a heat treatment (the above-mentioned annealing treatment) at a temperature in the range of 50 ° C. or more and the glass transition temperature or less after the stretching and before the application of the emulsion. The time required to perform the heat treatment is 0.1 to 15
00 hours is common. 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 heat treatment must be performed at a temperature lower than the glass transition temperature.

Using the above polyester film, 135
When a long photographic film such as a photographic film or a Broni type photographic film is prepared, a photographic layer composed of a protective colloid mainly composed of gelatin (for example, a photosensitive halide) is formed on a support because the polyester film has a hydrophobic surface. It is very difficult to firmly adhere the silver emulsion layer, the intermediate layer, the filter layer, etc.). 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 and an increase in the cross-linking density of the surface on the originally hydrophobic support 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 contrivances have been made for the constitution of the undercoat layer. A layer (hereinafter, abbreviated as first undercoat layer) that adheres well to the support is provided as a first layer, and a 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, methacrylic acid, acrylic acid, itaconic acid, including a copolymer starting from a monomer selected from maleic anhydride, starting with various polymers Can be used. In the second layer of the undercoat, gelatin is mainly used.

In the single-layer method, good adhesion is often achieved by swelling a large number of supports and interfacial 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. Among these, gelatin is most preferred. The binder of the back layer may be a hydrophobic polymer or a hydrophilic polymer as used in the undercoat layer. In the back layer, an antistatic agent, a lubricant, a matting agent,
Surfactants, dyes and the like can be contained. The most preferred antistatic agents are ZnO, TiO ₂ , Sn
O ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, B
Fine particles of at least one crystalline metal oxide selected from aO and MoO ₃ V ₂ O ₅ or composite oxides thereof.

The photographic film support of the present invention includes not only a polyester film but also a support having the above-mentioned undercoat layer. That is, the heat treatment may be performed after the formation of the undercoat layer, and such a support is also included in the present invention. Further, the physical properties and the like of the polyester film are not substantially changed by the formation of the undercoat layer.

Next, the photographic layer (silver halide emulsion layer) of the above 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 tetradecahedral, those having irregular crystalline forms such as spherical and plate-like, 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. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Even if the crystal structure is uniform,
The inside and outside may be made 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. The additives used in such a process are Research Disclosure Nos. 17643 and N
o. 18716. Various color couplers can be used in the photographic layer, and specific examples thereof are described in Research Disclosure (RD) No. 17 described above.
643, VII-CG.

The light-sensitive material is a total film thickness of all hydrophilic colloid layers on the side having emulsion layers is 28μm or less and the film swelling speed T _^1/2 is preferably 30 sec or less. 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 spool of the patrone for loading the 135 type film is usually 10 to 14 mm, particularly 11 to 13 mm. In the case of a Brownie type (120 type or 220 type) film, 11.2 to 12.1 mm
Is common.

[0038]

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.

Example 1 10 pellets of polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60
Dry at 0 ° C. under reduced pressure for 12 hours. Dried pellets,
The mixture was charged from a hopper into an extruder equipped with a 10 μm mesh filter. The polyester is melt-mixed in a heated extruder, and the molten polyester heated to 300 ° C. is melt-extruded in a sheet form from a T-die onto a casting drum having a surface temperature of 50 ° C., and an unstretched sheet having a thickness of 350 μm is formed. I got Next, the unstretched sheet is
After stretching at a temperature of 1.0 ° C. in the longitudinal direction (length direction) by 1.0 times (that is, transporting without stretching), and then cooling, 135
The film was stretched 3.0 times in the transverse direction (width direction) at a temperature of ° C, heat-set at 170 ° C, and cooled to produce a 105 µm-thick transversely stretched film. The transverse stretching was performed using a tenter type stretching machine.

Example 2 A biaxially stretched polyester film was prepared in the same manner as in Example 1, except that the longitudinal stretching conditions and the transverse stretching conditions were changed as shown in Table 1. I got

Example 3 A transversely stretched polyester film was obtained in the same manner as in Example 1, except that the heat setting conditions were changed as shown in Table 1.

[Comparative Examples 1 and 2] In the same manner as in Example 1, except that the longitudinal stretching conditions, the transverse stretching conditions, and the heat setting conditions were changed as shown in Table 1, A biaxially stretched polyester film was obtained.

Each of the obtained polyester films was wound and annealed at 100 ° C. for 24 hours. The obtained polyester film was evaluated as follows. (Measurement and Evaluation Methods) (1) Tear Resistance (g / mm) This was carried out in accordance with JIS P8116-1994 (Test method for tear strength of paper and paperboard). However, the test piece has a length of 51
One having dimensions of 64 mm and a width of 64 mm with a cut of 13 mm was used. As a measuring machine, a TSS type load tearing tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used.
The sample was torn in the width direction (lateral direction).
The unit was g / mm divided by the thickness of the film. (2) Loop stiffness (rigidity) The obtained polyester film was 20 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 15 mm from the outside (horizontal direction) was measured. This measurement was performed using "Loop Stiffness Tester" (manufactured by Toyo Seiki Seisaku-sho, Ltd.). The unit was expressed per 100 μm by dividing the obtained weight by the cube of the thickness of the film.

The main conditions for producing the above photographic film support and the evaluation results are summarized in Table 1 below.

[0045]

[Table 1] Table 1 フ ィ ル ム Film longitudinal stretching lateral stretching heat setting tearing Strength Loop stay Resin / thickness Magnification Temperature Magnification Temperature Temperature (width direction) Tifness (length direction) (μm) (° C) (° C) (° C) (g / mm) (g / 100μm) ────── ────────────────────────────── Example 1 PEN / 105 1.0 105 3.0 135 170 250 23 Example 2 PEN / 105 1.5 105 3.0 135 170 320 28 Example 3 PEN / 105 1.0 105 3.0 135 240 250 24 ─────────────────────────────── ───── Comparative Example 1 PEN / 105 3.0 105 3.0 145 240 650 33 Comparative Example 2 PEN / 105 2.7 105 3.3 145 240 600 32 ─────────────────── ─────────────────

Evaluations (3) to (6) described below were made after providing an undercoat layer and further providing an emulsion layer on the obtained polyester film as described below. After the polyester biaxially stretched film subjected to the annealing treatment as described above was subjected to a glow discharge treatment, an undercoat layer having the following composition was 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-speed photographic emulsion layer) is formed on the undercoat layer as follows, and a photographic film (light-sensitive material) is formed.
Was prepared.

The following surface-treated support was coated with the following undercoat layer-forming cloth solution at 10 ml / m ² and dried at 120 ° C. for 6 minutes. [Undercoat solution] Gelatin 1.0 part by weight Salicylic acid 0.3 part by weight Formaldehyde 0.05 part by weight pC ₉ H ₁₉ C ₆ H ₄ O (CH ₂ CH ₂ O) ₁₀ H 0.1 part by weight Distilled water 2.2 96.35 parts by weight of methanol 96.35 parts by weight After forming the undercoat layer, a back layer having the following composition was coated on the surface of the support opposite to the side on which the undercoat layer was provided. 3-1) 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 ethanol 300
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 to obtain a red-brown colloidal precipitate.

The red-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 was repeated three times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
00 parts by weight were redispersed in 1500 parts by weight of water and sprayed into a baking furnace heated to 600 ° C. to give a bluish average particle size of 0.1.
A fine particle powder of a tin oxide-antimony oxide composite of μm was obtained. The specific resistance of the fine particle powder was 25 Ω · cm.
The mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH
7.0, and after coarse dispersion with a stirrer, a horizontal sand mill (trade name: Dino Mill; WILLYA. BACHOFEN)
AG (manufactured by AG) and dispersed until the residence time became 30 minutes.

3-2) Preparation of Back Layer: Following Formula [A]
Is applied so that the dry film thickness becomes 0.3 μm.
For 60 seconds. Further, the following coating liquid (B) for a coating layer was applied so as to have a dry film thickness of 1 μm.
Dry at 5 ° C. for 3 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 quinyl phenyl ether 0.01 part 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 Silica particles (average particle size 0.2 μm) 0.01 parts by weight Polysiloxane 0.005 parts by weight C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (8/2 weight ratio) 0.01 part by weight Dispersion (average particle size 20 nm)

Coating of Photosensitive Layer Each layer having the following composition was coated on the support obtained by the above method to form a multilayer color light-sensitive 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 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.

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

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

Fifteenth 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 layer to improve the storability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability. 6, F
-1 to F-17 compounds and iron salts, lead salts, gold salts,
Contains platinum, iridium and rhodium salts.
Table 2 shows the composition of the emulsion used for each layer.

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[Table 2]

In Table 2, (1) Emulsions A to F were subjected to reduction sensitization during grain preparation 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 in each layer are shown.

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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.

(3) Cutability Using a patrone loaded with the obtained photographic film, the loaded photographic film was subjected to development processing by a small automatic developing machine. At that time, the film was cut in the width direction, and the cutting state at that time was observed. And the state of cutting was evaluated as follows. AA: Cutting was completely performed. BB: Partially cut, but not complete. CC: It was not cut, but only bent. (4) Unevenness of Development Using a patrone loaded with the obtained photographic film, the loaded photographic film was subjected to development processing by a small 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 (5) Generation of out-of-focus A patrone loaded with the obtained photographic film is loaded into a camera, and an actual photograph is taken. After development, the negative film is observed to observe out-of-focus. The presence or absence was investigated. AA: No out-of-focus occurred. BB: Out-of-focus occurred. (6) Handling after Loading into Camera A patrone loaded with the obtained photographic film was loaded into 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 3 shows the results obtained above.

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[Table 3] Table 3 ──────────────────────────────────── Cutability Development spots Out of focus Handling (jamming Example 1 AA AA AA AA Example 2 AA AA AA AA Example 3 AA AA AA AA 比較 Comparative Example 1 CC AA AA AA Comparative Example 2 CC AA AA AA Comparative Example 3 CC AA AA AA ─

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The support for a photographic film according to the present invention comprises 13
In addition to the properties required for a roll-shaped film such as a type 5 or a brownie film, such as being difficult to be rolled up, the cutability in the width direction is good, so that a photograph obtained using this support can be obtained. The film can be developed by a small automatic processor without any trouble. In addition, the photographic film does not have irregularities on the cut surface subjected to the slit processing or the perforation processing, and exhibits good workability. Furthermore, since the adhesiveness with the undercoat layer applied to the support surface is excellent, there is an advantage that the selection range of the undercoat layer forming material is expanded.

Claims (5)

[Claims] Claims: 1. More than 95 mol% of ethylene-2,6-
A long film made of a polyester having a repeating unit consisting of a naphthalate unit and less than 5 mol% of an ethylenebenzenedicarboxylate unit, further having a tear strength in the width direction of 400 g / mm or less, and a length direction. Has a loop stiffness of 50 g / 100 μm
A support for a long photographic film, characterized by the following: 2. The support according to claim 1, wherein the width of the film is 35 mm or more. 3. The film has a thickness of 90 to 130 μm.
The support for a long photographic film according to claim 1, which is: 4. The method according to claim 1, wherein the polyester is polyethylene-2,
2. The support according to claim 1, which is 6-naphthalate. 5. Ethylene-2,6-greater than 95 mol%
After melt-extruding a polyester having a repeating unit comprising a naphthalate unit and less than 5 mol% of an ethylenebenzenedicarboxylate unit into a sheet, the sheet is stretched in the extrusion direction at a stretch ratio of 2 or less while heating, and A method for producing a support for a long photographic film, comprising stretching in a direction perpendicular to the extrusion direction at a stretching ratio of 2.5 to 6 times.