JPH05307235A - Roll film cartridge for photography and film camera for photography - Google Patents

Abstract

PURPOSE:To provide the film cartridge for photography which lessens the deterioration in photographic characteristics during preservation in spite of a small size and has an excellent property to eliminate the permanent set of winding and the camera incorporating the film cartridge for photography. CONSTITUTION:This roll film cartridge P for photography has a film take-up shaft and a film take-up chamber and has a photographic film F which is wound around the take-up shaft and is housed in the film take-up chamber. The diameter D1 of a circle 8 inscribing the projection diagram of the inside wall of the film takeup chamber from the rotating direction of the film take-up shaft does not exceed 22mm and the effective diameter of the film take-up shaft is at least 6mm. The total thickness of a film base and photograph constituting layers is 100 to 140mum. The film base is formed of copolymerized polyester consisting of arom. dicarboxylic acid having a metal sulfonate group as a copolymer component and the content of the diethylene glycol in the copolymerized ester is <=5mol%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a small-sized photographic roll film cartridge and a photographic film camera having good portability, and more particularly to a photographic roll film cartridge which is small in size and improved in handling during development processing. The present invention relates to a photographic film camera incorporating such a photographic roll film cartridge.

[0002]

2. Description of the Related Art At present, as a negative film for amateurs, a roll film with a cartridge of 135 mm size occupies most of the market.
The 135 mm size cartridge system has drawbacks that it is difficult to load a film in a camera and the size is large, which is a restriction on camera design.

In recent years, downsizing and simplification of cameras have been advanced, portability has been improved, and photography meetings have been greatly increased.
Under such circumstances, further miniaturization of the camera is desired by users, and miniaturization while maintaining high image quality has been widely studied. And so-called 1 for general
Since the 35-size roll film is loaded in the standard format cartridge, it is an obstacle to making the camera thinner. In order to miniaturize the cartridge, it is most effective and convenient to thin the film, that is, the photosensitive material, and to achieve the miniaturization of the camera by making the support of the photosensitive material thinner than before. Should be possible.

Further, the standard size Patrone of 135 size is currently limited to 36 pictures. There is a desire to put more image information in one Patrone,
This can also be achieved by making the support of the photosensitive material thinner than before.

By the way, Japanese Unexamined Patent Publication No. 2-181749 discloses a small film cartridge having a film base thickness of 100 μm or less. However, even if the film base is set to 100 μm or less so that miniaturization of the camera can be achieved in this way, a curl occurs due to the film being placed for a long time in the small film cartridge. A film with a curl has a problem that it is difficult to handle in the developing process.
For this reason, there is a need for a film base which has the characteristic of being able to take a curl during development processing, which is a characteristic of a commonly used cellulose triacetate film base, and which has improved mechanical strength. Various film bases have been proposed to achieve such a purpose.

Such an example is disclosed in, for example, Japanese Patent Laid-Open No. 1-24444.
It can be found in Japanese Patent Publication No. 46 and the like.

However, it cannot be said that the film base described in the above publication has a sufficient curl eliminating property.
The present inventors have found that this problem becomes apparent especially when the film cartridge is small and the film winding shaft in the film cartridge is thin. Further, it has been revealed that there is an unexpected problem that the photographic characteristics of the film are deteriorated when the photographic film having the thin support is stored for a long period of time in a small film cartridge.

On the other hand, as disclosed in Japanese Patent Laid-Open No. 3-41435, it is known that when the film base is made thin to reduce the size of the film cartridge, the perforation portion is cut. The invention described in the publication attempts to solve this problem by providing a gelatin-containing backing layer, but the gelatin-containing backing layer is contaminated during the development process, which causes a fatal defect in a photographic image. The inventor has found that

Therefore, when the film base is thinned for the miniaturization of the cartridge, the winding tendency of the film,
No film patrone has been found which has no perforation discontinuity, does not stain the film during the development process, and has little deterioration of the photographic characteristics of the film.

An object of the present invention is to solve the above problems and to provide a roll film patrone for photography which is small in size, has little deterioration in photographic characteristics due to long-term storage, and is excellent in curl resolving ability, and such a photographic roll film cartridge. It is to provide a camera with a built-in roll film cartridge.

[0011]

The invention according to claim 1 for solving the above-mentioned problems has a film winding shaft and a film winding chamber, and is wound around the winding shaft and film winding. A roll film cartridge for photographic use having a photographic film housed in a chamber, wherein the diameter of a circle inscribed in the projection view of the film winding indoor wall from the rotation direction of the film winding shaft does not exceed 22 mm, and the film winding The effective diameter of the take-up shaft is at least 6 mm, and the total thickness of the film support and the photographic constituent layers is 100 to 140 μm.
m and the film support is formed of a copolymerized polyester having an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, and the diethylene glycol content in the copolymerized polyester is 5 mol% or less. The invention described in claim 2 is a roll film cartridge for photographic use, wherein the diameter of the winding shaft relative to the diameter of the circle inscribed in the projection of the inner wall of the film winding chamber from the direction of the rotation axis of the film winding shaft. The photographic roll film cartridge according to claim 1, wherein the ratio to the effective diameter is 1.3 to 2.1, and the invention according to claim 3 is the photographic roll film according to claim 1. It has both a cartridge and a shooting function, and is designed so that the photographic film is stored in the film winding room as the shooting is performed. It is a photographic film camera which is characterized.

The present invention will be specifically described below.

The film cartridge and the photographic film camera according to the present invention can be effectively used as, for example, a simple camera generally called a film unit with a lens.

In such a camera, the film is wound on the winding shaft side of a normal camera in advance, and the film is rewound into the patrone as it is photographed during use.

FIG. 1 is an explanatory perspective view showing such a film winding state. In the figure, F is a film, which is wound on the unwinding shaft S in advance before using the camera.

[0016] Then, it is a system in which the film is successively wound around the cartridge P for shooting.

FIG. 2 is a sectional view taken along a plane (horizontal section) orthogonal to the axial direction of the cartridge P. Figure 2
At the cartridge body part 6, the film outlet 7
Is provided along the axial direction, and the inner wall of the film take-out opening 7 is provided with a telem T for protecting the film. As shown in FIG. 2, the inner wall of the cartridge P is a cylindrical inner wall except for the portion where the outlet 7 is provided. When the horizontal cross section of the cartridge P is viewed, the inscribed circle 8 is hypothesized from the cylindrical inner wall. In the present invention, this virtual inscribed circle 8 is referred to as a circle inscribed in the projected view of the inner wall of the film cartridge winding room.
When the diameter of this circle is D ₁ , D ₁ does not exceed 22 mm, preferably 15 to 21 mm, particularly preferably 17 to 20 mm. In the present invention, D ₁
Is designed so as not to exceed 22 mm, and the winding shaft is at least 6 mm as will be described later, so that the object of the present invention can be achieved. On the contrary, when D ₁ exceeds 22, the photograph is obtained. It is not possible to reduce the size of the film camera for use. Further, even if D ₁ does not exceed 22 mm and the take-up shaft is less than 6 mm, it is possible to reduce the appearance of the photographic film camera, but the physical properties and photographic characteristics of the film deteriorate. ..

FIG. 3 is a sectional view of the cartridge of the present invention. In the figure, 1 is a long hub, 2 is a short hub, and 4
Indicates a flange, and 5 indicates a cap. 3 is a winding shaft, and 6 is a barrel. Effective diameter of D ₂ when the shaft diameter of the winding shaft 3 and D ₂ are both thin 6 mm, preferably 8～13Mm, particularly preferably 9~12mm
Is. When the winding shaft has a shaft diameter of 6 mm or more, even if the photographic film which is wound around the winding shaft has a winding tendency, the winding tendency can be easily eliminated.
When the thickness is less than mm, not only the curl attached to the photographic film which is wound around the winding shaft is not easily eliminated, but also the photographic characteristics are deteriorated.

Further, in the present invention, it is preferable that D ₁ / D ₂ is 1.3 to 2.1. When D ₁ / D ₂ is 1.3 to 2.1, the photographic roll film patrone of the present invention is produced by slightly modifying the conventional standard patrone production apparatus in the production of the photographic roll film patrone. It is possible to manufacture the photographic roll film cartridge of the present invention without significantly changing the conventional manufacturing equipment, which is an extremely great advantage from an industrial viewpoint. Further, even when handling photographic roll film cartridges collected from users at a film developing station, if D ₁ / D ₂ is within the above range, conventional processing equipment and processing equipment can be used as they are or a simple curing can be performed. The great advantage is that it can be dealt with by using tools and adapters. In particular, if D ₁ / D ₂ is less than 1.3, downsizing of the cartridge cannot be achieved, or the film storage volume becomes too small for practical use, or the film must be extremely thin. Therefore, it is difficult to handle.

If D ₁ / D ₂ exceeds 2.1, the cartridge cannot be downsized, or the winding shaft becomes too thin, and it becomes difficult to eliminate the winding tendency. It becomes difficult to join or wind the film on the take-up shaft.

Here, the effective diameter is defined as the thickest portion of the winding shaft around which the film is wound. The total thickness of the film base and emulsion layer is 80-140 μm
And preferably 90 to 138 μm. Total thickness is 8
When it is in the range of 0 to 140 μm, even if it is stored in the small photographic roll film cartridge of the present invention, it is possible to take “24 sheets”, which is widely used in the normal 135 size for shooting. The user has the advantage that they can shoot with peace of mind as if they were the number of shots taken,
The object of the present invention can be achieved. Total thickness is 80 μm
When the value is below the range, it causes misalignment in the film guide groove inside the ordinary camera, which is widely marketed, and the photographic constituent layers of the film are misaligned with the focus surface of the lens, so-called "unfocused" photos with poor sharpness. Will be obtained.

If the total thickness exceeds 140 μm, the above-mentioned advantage of “24 rolls” cannot be achieved, or the winding shaft must be made thin, which exposes the above-mentioned drawbacks.

The photographic film in the photographic roll film cartridge of the present invention is a film support formed of a copolyester having an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and a diethylene glycol content of 5 mol% or less. Have.

A preferred example of the copolymerized polyester is a copolymerized polyester having an aromatic dicarboxylic acid having a metal sulfonate group and a small amount of diethylene glycol as a copolymerization component and an aromatic dibasic acid and a glycol as main constituents. Can be mentioned.

Examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the glycols are ethylene glycol, propylene glycol, butanediol,
Examples include neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene fricol and the like. Among these, terephthalic acid is preferable as the aromatic dibasic acid, and ethylene glycol is preferable as the glycol.

Examples of the aromatic dicarboxylic acid having a metal sulfonate group include 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6.
-Naphthalenedicarboxylic acid, or an ester-forming derivative represented by the following (Chemical formula 1), and compounds obtained by substituting these sodiums with other metals such as potassium and lithium can be given.

[0027]

[Chemical 1]

The copolyester having an aromatic dicarboxylic acid having a metal sulfonate group can be detected by hydrolysis of the copolyester, and the amount of the aromatic dicarboxylic acid having a metal sulfonate group can be determined based on the total acid component. It is preferably 2 to 7 mol%. If the amount of the aromatic dicarboxylic acid having a metal sulfonate group is less than 2 mol%, the curl of the photographic film may not be sufficiently recovered, and if it exceeds 7 mol%, the film support may have poor heat resistance. May be.

The copolymerized polyester in the present invention is
It contains diethylene glycol in a proportion of 5 mol% or less. This amount of diethylene glycol is the value detected by hydrolyzing the co-weight polyester. By containing this ethylene glycol in a proportion of 5 mol% or less, the film support of the present invention is excellent in curl recovery, and moreover, various water-based coating liquids are applied to the surface of the film support. Even if the film is heat-treated at a high temperature, the reduction in the flatness of the film support can be prevented.

The copolymerized polyester in the present invention is
As long as it has an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and diethylene glycol, and does not impair the object of the present invention, polyalkylene glycol and / or C 4-20
The above aliphatic dicarboxylic acid may be contained as a copolymerization component.

As the polyalkylene glycol,
Examples thereof include polyethylene glycol and polytetramethylene glycol. What is important in the present invention is that polyethylene glycol is preferred among the polyalkylene glycols. Further, the molecular weight thereof is usually 600 to 20,000, and 1,000 to
It is preferably 5,000.

Examples of the aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, adipic acid, sebacic acid, etc. Of these, adipic acid is preferred.

When the copolyester having an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and diethylene glycol in the present invention contains an aliphatic dicarboxylic acid as a monomer unit, the copolyester is hydrolyzed. The amount of aliphatic dicarboxylic acid thus detected is usually 3 to 25 mol% based on all ester bonds. When the aliphatic dicarboxylic acid as a monomer unit is contained in the copolyester so that the amount of the aliphatic dicarboxylic acid is within the above range, the curl of the photographic film can be easily eliminated, and the film The support can have heat resistance in practical use.

The copolyester used in the present invention may have other types of monomer units as long as the object of the present invention is not impaired.

The copolyester having an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit is not particularly limited in its production method. For example, after transesterifying the dicarboxylic acid component and the glycol component, a high temperature is used. And polycondensation under reduced pressure.

Examples of the catalyst used in this transesterification include acetates, fatty acid salts, carbonates of metals such as manganese, calcium, zinc and cobalt. Among these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable.

It is also effective to add a hydroxide, a metal salt of an aliphatic carboxylic acid, a quaternary ammonium or the like to the extent that the reaction is not inhibited and the polymer is not colored during the transesterification and / or polycondensation. Among them, sodium hydroxide, sodium acetate and tetraethylhydroxyammonium are preferable, and sodium acetate is particularly preferable. The addition amount of these is 1 × 10 ^-2 to 2 with respect to all acid components.
0 × 10 ^-2 mol% is preferable.

The copolyester used in the present invention contains phosphoric acid, phosphorous acid,
And their esters and inorganic particles (for example, silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.), or the inorganic particles appropriately added after the polymerization.

Further, the copolyester may contain a dye, an ultraviolet absorber, an antioxidant, etc., which are appropriately added at any of the polymerization stage and the post-polymerization stage.

The film support in the present invention preferably contains a specific copolyester and an antioxidant.

The type of the antioxidant is not particularly limited, and specific examples thereof include hindered phenol compounds, allylamine compounds, phosphite compounds, thioester antioxidants and the like. .. Among these, hindered phenol compounds are preferable.

The content of the antioxidant in the film support is usually 0.01 to 2 with respect to the copolyester.
%, Preferably 0.1 to 0.5% by weight. If the content of the antioxidant is less than 0.01% by weight, the effect of photographic performance is inferior, and if it exceeds 2% by weight, the turbidity of the copolyester increases and it may not be preferable as a film support. The antioxidants may be used alone or in combination of two or more.

The film support according to the present invention is
For the purpose of preventing the light piping phenomenon (fogging) that occurs when light is incident on the film support provided with the photographic emulsion layer from the edge, it is preferable to incorporate a dye in the photographic support. The dye to be blended for such a purpose is not particularly limited in its type, but a dye having excellent heat resistance is preferable in the film forming process of the film, and examples thereof include anthraquinone chemical dyes. You can Further, as the color tone of the film support, gray staining is preferable as seen in general light-sensitive materials,
It is also possible to use one kind or a mixture of two or more kinds of dyes. SUMIPLAST manufactured by Sumitomo Chemical Co., Ltd. and Diare manufactured by Mitsubishi Kasei Co., Ltd.
Dyes such as sin and Bayer's MACROLEX can be used alone or in an appropriate mixture.

The film support of the present invention is, for example, selected from the group consisting of the above-mentioned copolyester, or an antioxidant optionally blended with this copolyester, or sodium acetate, sodium hydroxide and tetraethylhydroxyammonium. The copolyester composition containing at least one of the following is sufficiently dried, and then melt-extruded into a sheet form through an extruder, a filter and a die controlled at a temperature range of 260 to 320 ° C., and the molten polymer is rotated. It is cooled and solidified on a cooling drum to obtain an unstretched film. After that, the unstretched film is biaxially stretched in the machine direction and the transverse direction, and heat-fixed to produce the film.

The stretching conditions of the film cannot be uniformly specified because it varies depending on the copolymerization composition of the copolyester, but the stretching ratio in the temperature range from the glass transition temperature (Tg) of the copolyester to Tg + 100 ° C. in the machine direction. 2.5-6.0 times, Tg + 5 ° C to Tg + 50 in the lateral direction
The draw ratio is in the range of 2.5 to 4.0 times in the temperature range of ° C. The biaxially stretched film obtained as described above is usually heat set at 150 ° C. to 240 ° C. and cooled. In this case, if necessary, it may be relaxed in the vertical direction and / or the horizontal direction.

The film support of the present invention may be a single-layer film or sheet formed by the above-mentioned method, or may be a film or sheet of another material formed by a coextrusion method or a laminating method. It may have a multilayer structure in which a film or sheet formed by the method is laminated.

The thickness of the film support of the present invention thus obtained is not particularly limited, but is usually 50.
˜120 μm, preferably 60 to 115 μm. The local variation in the thickness of the film base is preferably within 5 μm, more preferably within 4 μm,
It is particularly preferably 3 μm or less. When the thickness of the film base is set within the above range, there is no problem in the strength and curling property of the film after coating the photographic constituent layer, and the film base can be contained within the total thickness range. Also, the local variation in the thickness of the film base is 5 μm.
Within the range, it is possible to prevent the occurrence of coating unevenness and the occurrence of drying unevenness when the photographic constituent layer is applied.

The photographic film of the present invention has a halogenated emulsion layer formed on one surface of the film support and a back layer formed on the other surface.

This silver halide emulsion layer comprises a silver halide emulsion containing silver halide and other components, directly or indirectly on the surface of one or both sides of a photographic support by dip coating, It can be formed by various methods such as air knife coating, curtain coating, and extrusion coating, by coating one layer at a time or multiple layers at the same time.

The silver halide emulsion can be coated directly on the film support or can be coated via another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion. Further, a hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, you may provide the intermediate layer which consists of hydrophilic colloids as needed. Further, between the silver halide emulsion layer and the protective layer, an intermediate layer, a protective layer,
A non-photosensitive hydrophilic colloid layer such as an antihalation layer or a back layer may be provided.

The silver halide used in the silver halide emulsion may have any composition.
Examples thereof include silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide and silver iodobromide.

Further, this silver halide emulsion may contain other components such as a binder, a sensitizing dye, a plasticizer, an antistatic agent, a surfactant and a hardener.

For the back layer, a back layer coating material containing gelatin and one or more other components to be blended, if necessary, is prepared by coating the surface of the film support on which the silver halide emulsion layer is formed. It can be formed by coating a single layer or a plurality of layers on the surface opposite to the surface.

In the present invention, it is preferable that the outermost layer of the back layer contains a fluorinated anionic surfactant and a fluorinated cationic surfactant.

[0055]

EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

(Examples and Comparative Examples) A. Preparation of Silver Halide Emulsion An octahedral silver iodobromide emulsion mainly having a (111) plane was prepared by the double jet method according to the method described in JP-A-60-138538.

The average grain size of the obtained emulsion was 1.05 μm,
The breadth of the distribution is 9%, the silver iodide content of the core is 30%, the silver iodide content of the shell is 0.1 mol%, the average silver iodide content is 9 mol%, and the ratio of (111) faces is Was 98%. This emulsion is called Em-101. In addition, Em having a similar shape and core / shell structure but different average particle size
-102 (0.71 μm), Em-103 (0.40 μm
m) was prepared. Em-102 and Em-103 were prepared by changing the amounts of the silver nitrate aqueous solution and the halide aqueous solution added to the seed crystal.

A tabular silver iodobromide emulsion mainly having a (111) plane was prepared by the double jet method according to the method described in JP-A-3-94248.

The average grain size of the obtained emulsion was 1.32 μm,
The average diameter / thickness ratio was 3.3, the projected area of particles having a diameter / thickness ratio of 2.0 or more was 96%, and the distribution width was 14%. The silver iodide content of the core was 30%, the silver iodide content of the shell was 0.1 mol%, the average silver iodide content was 9.0 mol%, and the ratio of (111) faces was 94%. . This emulsion is called Em-201. Also a similar shape and core /
Em-20 having a shell structure and different average particle sizes
2 (0.86 μm) and Em-203 (0.51 μm) were prepared. Em-202 and Em-203 were prepared by changing the amounts of silver nitrate aqueous solution and halide aqueous solution added to the seed crystal.

(Control of development starting point) In the process of chemical sensitization and color sensitization of the obtained emulsion, the sensitizing dye is added at the time of addition, that is, prior to the addition of the chemical sensitizer or the chemical sensitization. The position of the development start point was controlled depending on whether to add after completion.

<Sensitizer 1> Sodium thiosulfate <Sensitizer 2> Chloroauric acid (0.3 mg) and ammonium thiocyanate (N15 mg) <Methanol solution of sensitizing dye> SD-A (70 mg),
Methanol solution containing SD-B (70Mg) and SD-C (70Mg) <Stabilizer> ST-1 (1.0 g) Silver halide emulsion Em-101 (containing 1 mol of silver halide) at 55 ° C. and pAg of 8. After adjusting to 0, an aqueous solution of sensitizer 1 and an aqueous solution of sensitizer 2 were sequentially added while stirring, and aging was performed for 120 minutes. After aging, set the temperature to 4
The temperature was lowered to 0 ° C., a methanol solution of a sensitizing dye was added, stirring was further performed for 20 minutes, and finally, an antifoggant AF-1 and a stabilizer ST-1 were added.

Similar silver halide emulsion Em-10
2, Em-103, Em-201, Em-202, Em
-203 was also sensitized. The amounts of the sensitizer 1 and the sensitizer 2 are adjusted according to the change in the crystal size of the silver halide so that the highest photographic sensitivity can be obtained, and the amount of the sensitizing dye is also used. Was prepared according to the change in crystal size of.

The emulsion obtained by this method was a halogenated emulsion having a development starting point mainly on the (111) plane of silver halide crystals.

The silver halide emulsion Em-101 (containing 1 mol of silver halide) was adjusted to 55 ° C. and pAg of 8.0, and a methanol solution of a sensitizing dye was added while continuing stirring, and 2
It was aged for 0 minutes, and then an aqueous solution of sensitizer 1 and an aqueous solution of sensitizer 2 were sequentially added to perform aging for 90 minutes. Next, the antifoggant AF-1 was added to lower the temperature to 40 ° C., and finally the stabilizer ST-1 was added. The amounts of the sensitizer 1 and the sensitizer 2 were adjusted so that the highest photographic sensitivity was obtained.

Similar silver halide emulsion Em-10
2, Em-103, Em-201, Em-202, Em
-203 was also sensitized. The amounts of the sensitizer 1 and the sensitizer 2 are adjusted according to the change in the crystal size of the silver halide so that the highest photographic sensitivity can be obtained, and the amount of the sensitizing dye is also used. Was prepared according to the change in crystal size of.

The emulsion obtained by this method is a halogenated emulsion having a development starting point mainly in the vicinity of the vertices of silver halide crystals, and the length 1 of the side connecting adjacent vertices is 1 with respect to the center of the vertices. The distribution of the development start points contained in the circle having the length of / 3 was 82%.

SD-A, SD-B, SD-C, S
The chemical structures of T-1 and AF-1 are shown in (Chemical Formula 2).

[0068]

[Chemical 2]

B. Preparation of transparent support (Transparent support 1 in the invention) 0.1 part by weight of calcium acetate hydrate was added to 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. It was 28 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), polyethylene glycol (number average molecular weight: 3,000) were added to the obtained product.
0) 8 parts by weight, antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight and sodium hydroxide 0.02 parts by weight were added. Then gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain polyester.

The polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly cooled and solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the machine direction at 80 ° C., then 3.3 times in the transverse direction at 90 ° C. and then at 220 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm. The diethylene glycol content was 4 mol%.

This biaxially stretched film was used as a transparent support 1, and an undercoat layer was provided on both sides of this transparent support 1 as follows.

That is, 100 parts by weight of a resin liquid for an undercoat layer obtained by emulsion polymerization of the following composition, 0.2 part by weight of the following surfactant, hexamethylene-1,6-bis (ethyleneurea) An undercoat layer coating solution comprising 3 parts by weight and 900 parts by weight of water was applied so as to have a wet film thickness of 20 μm,
It was then dried. In the following, the transparent support having the undercoat layer may be simply referred to as a transparent support.

<Composition> 2-hydroxyethyl methacrylate 75 parts Butyl acrylate 90 parts t-Butyl acrylate 75 parts Styrene 60 parts Sodium dodecylbenzene sulfonate 6 parts Ammonium persulfate 1 part Water 700 parts <Surfactant>

[0074]

[Chemical 3]

Next, 10 parts by weight of gelatin and 0.
An undercoating upper layer coating liquid consisting of 2 parts by weight and 1,000 parts by weight of water was applied so as to have a wet film thickness of 20 μm, and then dried.

(Transparent support 2 in the present invention) In the production example of the transparent support described in the section of the transparent support 1 in the present invention, 0.07% by weight of tetraethylhydroxyammonium was added in place of sodium hydroxide. A biaxially stretched film having a thickness of 80 μm was obtained in the same manner as above. The diethylene glycol content was 5 mol%.

On both surfaces of this transparent support 2, an undercoat layer formed in the same manner as in the transparent support 1 is provided.

(Transparent support 3 in the present invention) In the production examples of the transparent support described in the section of the transparent support 1 in the present invention, 0.04% by weight of sodium acetate was used as an ester instead of sodium hydroxide. A biaxially stretched film having a thickness of 80 μm was obtained by the same method except that it was added during the exchange reaction. The diethylene glycol content was 3 mol%.

On both sides of this transparent support 3, an undercoat layer formed in the same manner as in the transparent support 1 is provided.

(Transparent support 4 in the present invention) To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate hydrate was added, and a conventional method was used. A transesterification reaction was performed. 32 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight), antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight were obtained. Parts and 0.04 parts by weight of sodium acetate were added. Then gradually raise the temperature and reduce the pressure to 280 ° C.,
Polymerization was performed at 0.5 mmHg to obtain polyester.

The polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the longitudinal direction at 80 ° C., then 3.3 times in the transverse direction at 90 ° C., and then at 200 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm.
The diethylene glycol content was 3 mol%.

On both sides of the transparent support 4, an undercoat layer formed in the same manner as in the transparent support 1 is provided.

(Comparative support 1 outside the scope of the present invention) To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate hydrate was added. The transesterification reaction was carried out by a conventional method. 32 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight) was added to the obtained product.
0.05 parts by weight of antimony trioxide and 0.13 parts by weight of trimethyl phosphate were added. Then gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain polyester.

This polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly cooled and solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the machine direction at 80 ° C., further stretched 3.3 times in the cross direction at 90 ° C., and then at 180 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm.
The diethylene glycol content was 9 mol%.

An undercoat layer formed in the same manner as in the transparent support 1 is provided on both sides of the comparative support 1.

(Comparative support 2) Dimethyl terephthalate 1
To 100 parts by weight of ethylene glycol and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added, and transesterification reaction was carried out by a conventional method. 28 parts by weight of an ethylene glycol solution (concentration: 35% by weight) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid was added to the obtained product.
8 parts by weight of polyethylene glycol (number average molecular weight 3000), 0.05 parts by weight of antimony trioxide, and 0.13 parts by weight of trimethyl phosphate ester were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was performed at 280 ° C. and 0.5 mmHg to obtain a polyester.

This polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the longitudinal direction at 80 ° C., then 3.3 times in the transverse direction at 90 ° C., and then at 200 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm.
The diethylene glycol content was 8 mol%.

An undercoat layer formed in the same manner as in the transparent support 1 is provided on both sides of the comparative support 2.

(Comparative Support 3) 100 parts of cellulose acetate (bound acetic acid content 61.4%) was dissolved in a mixed organic solvent of 550 parts of methylene chloride, 33 parts of methanol and 65 parts of cyclohexane, and triphenylphosphine was added to this solution. After 15 parts of fate and a small amount of dye were added and dissolved, the mixture was filtered and defoamed to prepare a cellulose acetate solution.

The cellulose acetate solution was cast from two casting ports located on an endless strip of 6 m stretched between two drums, and the casting layer was peeled from the stainless strip, and then it was rolled by a number of rolls. Drying was completed while being conveyed, and a cellulose acetate film having a thickness of 127 μm was produced.

On both sides of this cellulose acetate, a coating solution for an undercoat layer consisting of 20 g of gelatin, 40 g of water, 20 g of salicylic acid, 600 g of methanol, 1,200 g of acetone and 200 g of methylene chloride was applied, and dried to prepare Comparative Support 3 Got

C. Preparation of Silver Halide Color Light-Sensitive Material Each layer having the composition shown below was applied and formed on the transparent support or the comparative support in the present invention by a coating method described below to obtain a halogenated multi-layer color light-sensitive material. A silver color light-sensitive material was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g / m ² unit in terms of metallic silver for silver halide and colloidal silver, and g / m for couplers, additives and magenta. ^The amount added in ² units is shown in mol per mol of silver halide in the same layer for the sensitizing dye.

First layer: antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 1.23.

Second layer; intermediate layer Compound (SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27.

Third Layer; Low Sensitivity Red Sensitive Layer Silver iodobromide emulsion (average grain size 0.38 μm) (silver iodide content rate 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0 .27 μm) (silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.9 × 10 ⁻⁴ Sensitizing Dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan Coupler (CC-1) 0.021 DIR compound (D-2) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30.

Fourth Layer: Medium Sensitive Red Sensitive Layer Silver iodobromide emulsion (average grain size 0.52 μm) (Silver iodide content rate: 8.0 mol%) 0.62 Silver iodobromide emulsion (average grain size 0 0.38 μm) (silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.2 × 10 ⁻⁴ Sensitizing Dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan Coupler (CC-1) 0.030 DIR compound (D-2) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93.

Fifth layer; high-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm) (silver iodide content: 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1. 3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ⁻⁵ Cyan coupler (C-2) 0.12 Colored cyan coupler (CC -1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91.

Sixth layer; intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80.

Seventh Layer: Low Sensitivity Green Sensitive Layer Silver iodobromide emulsion (average grain size 0.38 μm) 0.61 (silver iodide content 8.0 mol%) Silver iodobromide emulsion (average grain size 0 0.27 (Silver iodide content 2.0 mol%) Sensitizing dye (SD-4) 7.4 × 10 ⁻⁵ Sensitizing dye (SD-5) 6.6 × 10 ⁻⁴ Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.33 Gelatin 1.95.

Eighth Layer: Medium-Sensitivity Green Sensitive Layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (S-6) 2.4 × 10 ^-4 Sensitizing dye (S-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.12 Magenta coupler (M-2) 0.06 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00.

Ninth layer: Medium-sensitive green-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol%) 1.27 Sensitizing dye (S-6) 1.4 × 10 ^-4 Sensitizing dye (S-7) 1.4 × 10 ^-4 Magenta coupler (M-1) 0.10 Magenta coupler (M-2) 0.05 Colored magenta coupler (CM-2) 0.012 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00.

10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10.

Eleventh layer; Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60.

Twelfth layer; low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm) 0.22 (silver iodide content 8.0 mol%) Silver iodobromide emulsion (average grain size 0 .27 μm) 0.03 (silver iodide content 2.0 mol%) Sensitizing dye (SD-8) 4.2 × 10 ⁻⁴ Sensitizing dye (SD-9) 6.8 × 10 ⁻⁵ Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20.

Thirteenth layer; low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm) 0.30 (silver iodide content 8.0 mol%) Sensitizing dye (SD-8) 1. 6 × 10 ⁻⁴ Sensitizing dye (SD-10) 7.2 × 10 ⁻⁵ Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0. 046 Gelatin 0.47.

Fourteenth layer: high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm) 0.85 (silver iodide content rate: 8.0 mol%) Sensitizing dye (SD-8) 7. 3 × 10 ⁻⁵ Sensitizing dye (SD-10) 2.8 × 10 ⁻⁵ Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80.

Fifteenth layer; first protective layer Silver iodobromide (average grain size: 0.08 μm) 0.40 (silver iodide content: 1.0 mol%) UV absorber (UV-1) 0.026 UV ray Absorbent (UV-2) 0.013 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31.

Sixteenth layer; second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 ..

The above-mentioned light-sensitive material further comprises compounds SU-1, Su-2, a viscosity modifier, a hardener H-1, and a hardener H-.
2, stabilizer ST-1, antifoggant AF-1, AF-2
(With a weight average molecular weight of 10,000 and 1,100,
000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg / m ² ).

The above UV-1, Oil-1, SC-1,
Oil-2, SD-1, SD-2, SD-3, SD-
4, C-1, C-2, CC-1, D-1, D-2, M-
A, CM-1, D-3, CM-2, SC-2, HS-
1, SD-5, Y-1, SD-6, UV-2, WAX-
1, SU-1, Su-2, H-1, H-2, ST-1,
The structures of AF-2, AI-1, AI-2 and compound DI-1 are shown in Chemical Formulas 4 to 11 below.

[0112]

[Chemical 4]

[0113]

[Chemical 5]

[0114]

[Chemical 6]

[0115]

[Chemical 7]

[0116]

[Chemical 8]

[0117]

[Chemical 9]

[0118]

[Chemical 10]

[0119]

[Chemical 11]

C. Film Patrone A silver halide color light-sensitive material having a layer thickness shown in Table 1 was prepared by providing the above-mentioned light-sensitive layer on each of the various supports, and sample numbers were given as shown in Table 1. Each sample was cut into the same width as a standard 35 mm standard, provided with perforations on both sides, and cut into a length such that 24 frames could be photographed. The obtained film had the structure shown in FIG. It was stored in a small cartridge having the size shown in Table 2. The sample numbers and the Patrone numbers are associated with each other in Table 1, and the Patrone numbers and various sizes of the Patrone indicated by the numbers are associated with each other in Table 2.

[0121]

[Table 1]

[0122]

[Table 2]

The above cartridge was heated and humidified in an atmosphere of 55 ° C. and 60% RH for 4 hours, and a test pattern was photographed with a small camera. Separately, the same Patrone was photographed with a small camera without the heating and humidifying treatment. NCV manufactured by Noritsu Koki Co., Ltd. according to the development processing steps described below for the photographed silver halide color light-sensitive material in each of the heated and humidified cartridges and the unheated cartridges.
It was developed with an -36 automatic processor.

D. Development Process Table 3 shows the details of the development process.

[0125]

[Table 3]

In Table 1, the replenishment amount is 1 m of the photographic light-sensitive material.
It is a value per ² . As the color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof, those prepared as described below were used.

<Color developer> Water 800 ml Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4- Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter and potassium hydroxide or 20
The pH was adjusted to 10.06 with% sulfuric acid.

<Color development replenisher> Water 800 ml Potassium carbonate 35 g Potassium sulfite 5 g Potassium bromide 0.4 g Hydroxylamine sulphate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter and potassium hydroxide or 20
The pH was adjusted to 10.18 with% sulfuric acid.

<Bleach> Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid disodium 2 g Sodium nitrate 40 g Ammonium bromide 200 g Glacial acetic acid 40 ml Water was added to make 1 liter, and then ammonia water or The pH was adjusted to 4.4 using glacial acetic acid.

<Bleach Replenisher> Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid disodium 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Water was added to make 1 liter, and aqueous ammonia was added. Alternatively, glacial acetic acid was used to adjust the pH to 4.0 and the pH of the bleaching tank liquid was appropriately adjusted.

<Fixer> Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, water was added to make 1 liter.

<Fixing Replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid disodium 2 g Ammonium water or glacial acetic acid was used to adjust the pH to 6.5 and water was added to make 1 liter.

<Stabilizing Solution and Stable Replenishing Solution> Water 900 ml p-Octylphenol ethylenoxide 10 mol adduct 2.0 ml Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, ammonia water or 50
The pH was adjusted to 8.5 with% sulfuric acid.

E. Evaluation The developed silver halide color light-sensitive material was evaluated as follows.

<Photographic characteristics during long-term storage> The density of the cyan image of the test pattern of each of the developed samples was measured,
The relative sensitivity value (%) of the unheated sample subjected to the heating / humidification treatment was determined. The larger the relative sensitivity value is, the better the long-term storage property is.

This test is forcibly carried out in a short period of time under severe conditions, and the situation of long-term storage is simply estimated and evaluated. The results are shown in Table 4.

<Removal of curl> The developed silver halide color light-sensitive materials thus obtained were put in a 135 size standard screen 3
The pieces were cut into pieces each having a length corresponding to a frame and placed on a horizontal plane with the photographic constituent layer side up in an atmosphere of 123 ° C. and 55% RH, and the state of curl (curl in the length direction) was observed. Then, the height of the sample end portion in the length direction from the horizontal plane is L ₁
And the height of the other end from the horizontal plane is L ₂ (L ₁ + L
₂ ) / 2 was evaluated. The results are shown in Table 4.

Comparative Example A A comparative support 4 was prepared in the same manner except that the thickness of the comparative support 3 in the above example was changed to 80 μm. A sample 119 was prepared by loading 1001. Photographing was carried out in the same manner as in the above-mentioned Examples, development processing was carried out, and the perforation portion was observed together with the samples 101 to 118.
There was a break in perforation only in 19, but
No such occurrence was observed in the other samples.

[0139]

[Table 4]

[0140]

According to the present invention, while being compact,
It is possible to provide a photographic film cartridge and a camera incorporating the photographic film cartridge, in which deterioration of the photographic characteristics upon storage is small and the curl eliminating property is excellent.

[Brief description of drawings]

FIG. 1 is a perspective view showing a winding state of a film.

FIG. 2 is a sectional view of a cartridge body portion.

FIG. 3 is a sectional view of a cartridge.

[Explanation of symbols]

 P Patrone S Unwinding shaft T Telemp 1, 2 Hub 3 Winding shaft 4 Flange 5 Cap 6 Body

Claims (3)

[Claims] 1. A photographic roll film cartridge having a film winding shaft and a film winding chamber, and having a photographic film wound on the winding shaft and housed in the film winding chamber. The diameter of the circle inscribed in the projection of the film winding chamber inner wall from the rotation direction of the shaft does not exceed 22 mm, and the effective diameter of the film winding shaft is at least 6 mm, and the film support and the photographic constituent layer are The total thickness is 100 to 140 μm, and the film support is formed of a copolymerized polyester having an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, and the diethylene glycol content in the copolymerized polyester is 5 mol% or less. A photographic roll film patrone characterized by being present. 2. The ratio of the effective diameter of the winding shaft to the diameter of the circle inscribed in the projection of the inner wall of the film winding chamber in the direction of the axis of rotation of the film winding shaft is 1.3 to 2.1. The photographic roll film cartridge according to claim 1, wherein 3. A photographic film having both the photographic roll film cartridge according to claim 1 and a photographing function, which is designed so that the photographic film is stored in a film winding chamber upon photographing. Film camera for.