JPH06138580A - Film - Google Patents

Abstract

PURPOSE:To obtain the film excellent in brittleness, transparency and antistatic property by imparting the silver halide emulsion layer on the one surface of the layer consisting of copoly merized polyester and the layer containing specified vanadium pentoxide on the other surface. CONSTITUTION:The film has the silver halide emulsion layer on the one surface of the layer consisting of copolymerized polester and the one layer containing vanadium pentoxide on the other surface, and the load of the vanadium pentoxide is 0.1-50mg/m<2>. When the load is below 0.1mg/m<2>, the film becomes inferior in electrical conductivity, and when the load is above 50mg/m<2>, the film becomes inferior in transparency and brittleness. The vanadium pentoxide can be applied at every part of the photographic material. That is, the vanadium pentoxide can be incorporated in all of a undercoat layer, a back layer and a hydrophilic coloid layer. The additives such as a surfactant, a mat material, a lubricant and a crosslinking agent excepting a binder are incorporated at the time of applying the vanadium pentoxide at need.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic film, and more particularly to a film excellent in transparency, brittleness and antistatic property.

[0002]

2. Description of the Related Art Conventionally, polyester films have been used for various purposes, but they are inconvenient in terms of handleability because they are easily charged with static electricity and are curled.

In recent years, a compact camera has been put into practical use, which allows easy photographing and is convenient to handle and carry.

However, considering that it is convenient and easy to carry,
Further miniaturization is desired, but in pursuit of miniaturization, it is indispensable to miniaturize the storage space of the photographic film contained therein. Normally, as a photographic film, a roll of film wound on a spool is built in, so in order to make the space compact and to secure a certain number of shots (for example, 36 shots), It is necessary to reduce the thickness of the photographic film itself.
In particular, the thickness of the photographic film support is currently 120-125.
Since it is about μm, which is considerably thicker than the thickness of the photosensitive layer (about 20 μm) above it, reducing the thickness of this support is the most effective in reducing the thickness of the entire photographic film. Considered a means. By the way, a triacetate film such as triacetyl cellulose (TAC) is typical as a plastic film support that has been conventionally used, but it is impossible to make it thinner than the current one because the mechanical strength of the TAC film is originally weak. Is.

On the other hand, polyethylene terephthalate has hitherto been known as a support and has been used for X-ray films and plate-making films. Due to its excellent strength, application to color negative films is also possible. However, although the polyethylene terephthalate support is excellent in strength, it has a drawback in that the once wound curl cannot be removed even after the development processing.

As a means for eliminating the curling of the polyester support, a method of making the polyester support hydrophilic has been considered. For example, JP-A-2-120857 and JP-A1-244446 disclose a method of making the polyester support hydrophilic. Improved techniques are shown.

However, these polyester films are
Easily charged due to friction and peeling, dust suction, electric shock,
It is known to cause various problems such as ignition. For example, in the case of a silver halide photographic light-sensitive material using a polyester film as a support, in the process of winding, rewinding, coating various kinds of coating layers including the photosensitive layer, and conveying during drying, etc. The material is charged by friction and peeling from the substance, and when the material is discharged, the photographic light-sensitive material is exposed to light and static marks are generated.

The generation of such static marks seriously impairs the commercial value of the photographic film and, in some cases, completely loses the commercial value. Also, when static electricity is accumulated in this way, it becomes easier for dust to adhere to the film surface,
In addition, it may cause a secondary failure such that uniform coating cannot be performed.

The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more remarkable as the sensitivity of the photographic light-sensitive material is improved and the processing speed is increased.

In particular, recently, the number of opportunities to undergo harsh handling such as high sensitivity of photographic light-sensitive materials and high-speed coating, high-speed photographing, high-speed automatic processing, etc., has increased the tendency for static marks to occur more and more.

Conventionally, in order to improve a charging failure, a method has been adopted in which conductivity is improved and the accumulated charge is dissipated in a short time before the accumulated charge is discharged. Antistatic agents that can be used, for example, U.S. Pat.No. 2,118,059,
No. 2,139,778, No. 2,982,651 and No. 2,591,590, the surfactants and U.S. Pat.
2,484, 2,725,297, 3,033,679 and 2,71
Polymers and the like described in each specification of No. 0,402 are known. However, since many of these substances have a humidity dependency in their electrical conductivity, there is a major drawback that they lose their function as a conductive layer under low humidity.

To solve such a problem, JP-A-56-143431 discloses a technique in which tin oxide is used as an antistatic treatment agent.

However, when this is applied to a hydrophilic copolyester film, there is a drawback that the brittleness is poor and the transparency is lost.

[0014]

It is an object of the present invention to provide a film having excellent brittleness, transparency and antistatic property.

[0015]

The above object of the present invention is to provide a layer comprising at least one silver halide emulsion layer on at least one side of a layer made of a copolyester and at least one layer containing vanadium pentoxide on at least one side. A film comprising, wherein the amount of vanadium pentoxide is
Achieved with films that are 0.1 to 50 mg / m ² .

The contents of the present invention will be described in more detail below.

With respect to vanadium pentoxide used in the present invention, those described in US Pat. No. 4,203,769, page 4 or page 9, are preferably used, and silver-doped one is particularly preferable.

In the present invention, the amount of vanadium pentoxide added is
It is 0.1 to 50 mg / m ² .

When the coating amount is less than 0.1 mg / m ² , the conductivity is poor, and when it is more than 50 mg / m ² , the transparency and brittleness are poor.

In the present invention, vanadium pentoxide can be applied to any part of the photographic light-sensitive material. That is, it can be contained in any of the undercoat layer, the back layer and the hydrophilic colloid layer.

When applying vanadium pentoxide, a surfactant, a matting agent, a slip agent, a binder, a binder, and
You may contain additives, such as a crosslinking agent.

Examples of the surface active agent include natural surface active agents such as saponin, nonionic surface active agents such as alkylene oxide type, glycerin type and glycidol type, carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester, phosphoric acid ester. And anionic surfactants containing an acidic group such as.

As the cross-linking agent, a so-called hardener for photographic gelatin, for example, aldehyde compounds such as formaldehyde and glyoxal, mucohalogen acid (Cl, Br), tetramethylene-1,4-bis (ethyleneurea), hexa Compounds having ethyleneimine groups such as methylene-1,6-bis (ethyleneurea), methanesulfonic acid esters such as trimethylene-1,3-bismethanesulfonic acid ester, bisacryloylurea, methaxylenevinylsulfonic acid, etc. Vinyl compounds, active halogen compounds such as 2-methoxy-4,6-dichlorotriazine and 2-sodiumoxy-4,6-dichlorotriazine, compounds having an epoxy group such as bisphenol glycidyl ether, isocyanate carboxyl group active type compounds And epoxy compounds can be used. Among these, a compound having an ethyleneimine group, a methanesulfonic acid ester, an epoxy compound and a compound having an active halogen are particularly preferable.

If necessary, the back layer of the present invention may contain a matting agent, a slip agent, a surfactant, a dye, a thickener, a polymer latex and the like.

Regarding these matting agents, slip agents, surfactants and hardeners, research disclosure (Resear
ch Disclosure), 17643, (1978) X term, X term, X
The items described in the items and the items X can be arbitrarily used.

The copolymerized polyester in the present invention is a copolymerized polyester containing an aromatic dibasic acid and glycol as main constituents. Examples of aromatic dibasic acids include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acids, and examples of glycols include ethylene glycol, propylene glycol, butanediol,
Examples include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol and p-xylylene glycol.

Of these, copolymerized polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents is preferable.

Examples of the aromatic dicarboxylic acid having a metal sulfonate group include 5-sodium sulfoisophthalic acid and 2-sodium sulfoisophthalic acid.
Sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid or its ester-forming derivatives, and compounds obtained by substituting these sodium with other metals (potassium, lithium, etc.) Used.

The copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate group is preferably 2 to 7 mol% with respect to the total acid component.

The copolymerized polyester used in the present invention further comprises polyalkylene glycol as a copolymerization component in an amount of 3 to 10% by weight based on the total weight of the copolymerized polyester.
It is preferable to contain.

Examples of the polyalkylene glycol include polyethylene glycol and polytetramethylene glycol. Among them, polyethylene glycol is preferable, and the molecular weight is not particularly limited, but 300 to 20000, preferably 600 to 10000, and particularly preferably 1000 to It is 5,000.

Further, Japanese Patent Laid-Open Nos. 1-244446 and 1-291248,
1-298350, 2-89045, 2-93641, 2-181749
No. 2-214852 and JP-A-2-291135, USP5138024.
It is also possible to use a copolyester film having a high water content as shown in the above.

The use of the film of the present invention is not limited, and it can be used as a packaging material, an electrical insulating material, an electrophotographic material, a base material such as OHP, etc., but it has at least one silver halide emulsion layer. It is particularly preferable to use it in a silver halide photographic light-sensitive material.

The copolymerized polyester used in the present invention may be further copolymerized with other components or may be blended with other polymers, as long as the effects of the present invention are not impaired.

In the polyester layer of the present invention, a matting agent, an antistatic agent, a lubricant, a surfactant, a stabilizer, a dispersant, a plasticizer, a UV absorber, a conductive substance, a tackifier, a softening agent,
A fluidity imparting agent, a thickening agent, an antioxidant and the like can be added.

The copolymer polyester film used in the present invention may contain various additives. For example, a dye can be added to the polyester film for the purpose of preventing a light piping phenomenon (fogging) which occurs when light is incident on the film coated with the photographic emulsion layer from an edge. The type of dye added to the film is not particularly limited, but a dye having excellent heat resistance in the polyester film forming process is preferable, and examples thereof include anthraquinone-based chemical dyes.

As for the color tone of the film, gray dyeing is preferable as seen in general light-sensitive materials, and one kind or two or more kinds of dyes may be mixed and used. It is also possible to achieve the target by using dyes such as Diaresin manufactured by Mitsubishi Kasei Co., Ltd. and MACROLEX manufactured by Bayer Co. alone or in an appropriate mixture.

The polymer used may contain phosphoric acid, phosphorous acid and esters thereof and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.) at the polymerization stage. After the polymerization, inorganic particles may be blended with the polymer. Further, a pigment, an ultraviolet absorber, an antioxidant and the like may be added appropriately at any stage of the transesterification reaction stage, the polymerization stage and the post-polymerization stage.

The copolyester used in the present invention is not particularly limited in its production method. For example, when a polycondensation reaction is carried out after an ester exchange reaction, an aromatic dicarboxylic acid having a polyethylene glycol or a metal sulfonate group during the transesterification reaction. A polycondensation component such as the above may be added and polycondensation may be continued, or a polycondensation reaction may be performed by adding these copolymerization components after the transesterification reaction.

The method for producing the film of the present invention will be described.

The unstretched sheet may be obtained by a conventionally known method. For example, after sufficiently drying the obtained resin, it is melt-extruded into a sheet through a filter and a die and cast on a rotating cooling drum to be cooled and solidified. There is a method.

The method of biaxially stretching the finished sheet is not particularly limited, but for example, the following method (A), (B) or (C) can be adopted.

(A) A method in which an unstretched sheet is first stretched in the longitudinal direction and then stretched in the transverse direction (B) A method in which an unstretched sheet is stretched in the transverse direction first and then in the longitudinal direction (C) Unstretched A method in which the sheet is stretched in the longitudinal direction in one stage or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction. The stretching is performed in order to satisfy the mechanical strength and dimensional stability of the film support. The ratio is preferably 4 to 16 times.

The intrinsic viscosity of the copolymerized polyester used in the present invention is 0, when measured at 20 ° C. in a mixed solution of phenol / 1,1,2,2-tetrachloroethane (60/40 weight ratio).
It is preferably 4-1.0, more preferably 0.5-0.8
Is.

When a silver halide emulsion layer and / or a gelatin back layer and the like are coated on the copolyester support, these are removed from the support by using pancreatin or an aqueous solution of sodium hypochlorite. It can be measured after peeling.

The thickness of the support of the present invention may be such that the required strength can be obtained depending on the application, for example, 50 to 110 μm.
A value in the range of m, preferably 60 to 100 μm, is preferable for obtaining a thickness and strength superior to those of conventional photographic supports.

The photographic support film of the present invention may be laminated with other substances by a coextrusion method or a laminating method within a range not impairing the effects of the present invention, and may be before, during or after stretching. Any of them may be laminated by a coating method.

The photographic support film of the present invention particularly preferably contains at least one silver halide emulsion layer on at least one side of the photographic support. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support. The silver halide emulsion can be coated directly on the support or can be coated through another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the 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 made of a hydrophilic colloid may be provided between the silver halide emulsion layers, if necessary. Also, between the silver halide emulsion layer and the protective layer,
A non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer and a backing layer may be provided.

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

A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide emulsion used in the present invention.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James The Theory of the Photographic Process, Fourth Editi
on) Pages 291 to 334 and the Journal of the America Chemical Society
n Chemical Society) 73, 3100 (1951).

[0053]

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

[Preparation of vanadium pentoxide a] Vanadyl ethoxide and VO (C ₂ H ₅ O) ₃ were dissolved in ethanol (special grade reagent) and mixed.

To this, water was added in an amount of 10 times the required amount of hydrolysis as an aqueous ethanol solution ([C ₂ H ₅ OH] / [H ₂ O] molar ratio was 5), and the mixture was stirred and mixed. After mixing container (Erlenmeyer flask)
Was tightly closed and left at room temperature. After gelation, a part of the sample was taken out, placed in a glass dish, and dried at room temperature (dry gel).

[Preparation of silver vanadium pentoxide dope b] 100 g of powdery vanadium pentoxide and 0.5 g of silver oxide were uniformly mixed. The resulting mixture, weighing 40 g, was placed in a platinum crucible and heated in a muffle furnace at 1000 ° C. for 5 minutes. Then, 1 l of distilled water was rapidly poured into it with vigorous stirring. The colloidal dispersion was diluted with water until the concentration of antistatic substance was 0.1% by weight.

[Preparation of Crystalline Metal Oxide Fine Particles c] 100 parts by weight of stannic oxide (average particle size 1.0 μm) 10 parts by weight of a 10% methanol solution of antimony trioxide 10 parts by weight A mixture of 50 parts by weight of methanol was added for over 10 minutes. Sonicated to obtain a uniform dispersion.

The dispersion was dried at 10 ° C. for 1 hour and then dried in air.
Firing at 800 ° C. for 1 hour gave stannic oxide.

The average particle size was 1.0 μm.

[Production of Support] (Support 1) 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.

28 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), polyethylene glycol (PEG) (number average molecular weight: Mw 3000) 8.1 was added to the obtained product. Parts by weight, 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 carried out at 280 ° C. and 0.5 mmHg to obtain a copolyester.

290 ° C. from the T-die using the obtained polymer
The film was melt-extruded into a film and rapidly cooled on a cooling drum to obtain an unstretched film (thickness: 870 μm). This unstretched film is preheated to 80 ° C, longitudinally stretched (3.2 times), and then the temperature 90
Lateral stretching (3.2 times) was performed at 0 ° C, and heat setting was performed at 210 ° C to obtain a support 1 having a film thickness of 85 µm.

(Support 2) 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate and 0.03 part of antimony trioxide. Part by weight was added, and transesterification was carried out by a conventional method.

To the obtained product, 0.05 parts by weight of phosphoric acid trimethyl ester was added, and the temperature was gradually raised and the pressure was reduced to 280
Polymerization was carried out at a temperature of 1 mmHg or less to obtain a copolyester.

Using the obtained polymer, T-die at 280 ° C.
The film was melt-extruded into a film and rapidly cooled on a cooling drum to obtain an unstretched film (thickness: 870 μm). This unstretched film is preheated to 80 ° C, longitudinally stretched (3.2 times), and then the temperature 90
The film was transversely stretched (3.2 times) at 0 ° C. and further heat set at 200 ° C. to obtain a support 2 having a film thickness of 85 μm.

(Support 3) 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol are added to 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation;
SIP) ethylene glycol solution (concentration 35% by weight) 22
Parts by weight (4 mol% / total acid component), polyethylene glycol (abbreviation: PEG) (number average molecular weight: 1000) 11 parts by weight (8.5% by weight / polymer), sodium acetate 0.05 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight As an antioxidant, Irganox 1010 (manufactured by CIBA-GEIGY) was added and mixed in an amount of 0.5% by weight based on the product polymer. Then, with stirring, manganese acetate as a catalyst
0.05 parts by weight and 0.05 parts by weight of antimony trioxide were added.

Thereafter, the temperature is gradually raised and the pressure is reduced to 270 ° C. and 0.5
Polymerization was performed at mmHg to obtain a copolyester.

280 ° C. from T-die using the obtained polymer
The film was melt-extruded into a film and rapidly cooled on a cooling drum to obtain an unstretched film (thickness: 870 μm). This unstretched film is preheated to 80 ° C, longitudinally stretched (3.2 times), and then the temperature 90
The film was transversely stretched (3.2 times) at 0 ° C. and further heat set at 200 ° C. to obtain a support 3 having a film thickness of 85 μm.

Example 1 [Preparation of Light-Sensitive Material]
A corona discharge treatment of W / m ² · min was applied, and the undercoating coating solution B-3 described below was applied to one surface as a subbing layer B-3 so that a dry film thickness was 0.8 μm, and a support was sandwiched. On the side opposite to the subbing layer B-3, the coating amount of the metal oxide in the subbing coating solution B-4 shown below is shown in Table 1.
Was added as shown in (4) and coated as an undercoat layer B-4 so as to have a dry film thickness of 0.8 μm.

<Undercoating coating liquid B-3> Copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content 30%) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1,000ml <Undercoating liquid B-4> Metal oxide 40% by weight of butyl acrylate, Copolymer latex solution of styrene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish with water 1,000 ml Furthermore, 8 W / on the undercoat layer B-3 and the undercoat layer B-4.
(M ² · min) corona discharge, undercoat layers B-3 and B
-4 was coated with the following coating solution B-5 to a dry film thickness of 0.1 μm to form an undercoat layer B-5.

<Coating Liquid B-5> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Finish with water The structures of the compounds (UL-1 to 3) used in 1,000 ml are collectively shown below.

On the undercoat layer B-5, 25 W / (m ² · mi
n) was subjected to corona discharge. Further, the following emulsion layers and the like are sequentially formed on the surface of the undercoat layer B-3 side, and the following back layer is sequentially formed on the surface of the undercoat layer B-4 side to prepare a silver halide photographic light-sensitive material 1. did.

The following numerical indications in <back layer> and <emulsion layer> indicate amounts per m ² .

<Back Layer> First Layer; Gelatin 4.5 g Sodium-di- (2-ethylhexyl) -sulfosuccinate 1.0 g Sodium tripolyphosphate 76 mg Citric acid 16 mg Carboxyalkyl dextran sulfate 49 mg Vinyl sulfone type hardener 23 mg 2 layers (outermost layer); gelatin 1.5 g Polymer beads (average particle size: 3 μm, polymethylmethacrylate) 24 mg Sodium-di- (2-ethylhexyl) -sulfosuccinate 15 mg Carboxyalkyl dextran sulfate 12 mg Vinyl sulfone type hard film Agent 30 mg Mixture of compounds SB-2 and SB-3 (molar ratio 1: 1) 45 mg Compound SB-1 200 mg <Emulsion layer> First layer; Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV- 1) 0.20 g Compound (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent ( il-2) 0.20 g gelatin 1.6 g second layer; intermediate layer (IL-1) gelatin 1.3 g third layer; low-sensitivity red-sensitive emulsion layer (RL) silver iodobromide emulsion (average grain size 0.3 μm, average iodine Content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.50 g Cyan Coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g 4 layers; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) ) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL -2) Gelatin 0.8 g Sixth layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average grain size) 0.3 μm, average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ⁻⁴ (mol / silver) 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point Medium (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye ( S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 ( Mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) ) 0.35g Gelatin 1.0g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1g Additive (HS-1) 0.07g Additive (HS-2) 0.07g Additive (SC-1) 0.12g High boiling point Solvent (Oil-2) 0.15 g Gelatin 1.0 g 9th layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm , Average iodine content 2.0 mol%) 0.25 g silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.25 g sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver) 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3g 10th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10) 3 × 10 ^-4 (Mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil) -2) 0.05 g gelatin 2.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g Ultraviolet absorber (UV- 1) 0.07g UV absorber (UV-2) 0.10g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling solvent (Oil-1) 0.07g High boiling solvent (Oil-3) 0.07g Gelatin 0.8g 12th layer; 2nd protective layer (PRO-2) Compound (Compound A) 0.04g Compound (Compound B) 0.004g Polymethylmethacrylate (average particle size: 3 μm) 0.02g Methylmethacrylate: ethyl Methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13 g Gelatin 0.7 g-Preparation of silver iodobromide emulsion-iodobromide used in the 10th layer The silver emulsion was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodisperse silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content 2 mol%) as seed crystals.

A solution <G-1> having the following composition was heated at a temperature of 70 ° C. and p
The seed emulsion responsible for 0.34 mol was added while maintaining Ag 7.8 and pH 7.0 while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, a solution <H-1> having the following composition and a solution <S-
1> and 1> were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining the pH at 10.1 and the pH at 6.0.
-2> was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them.
H and pAg were adjusted to 5.8 and 8.06, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Solution Ocein gelatin 100.0 g 10% by weight solution of the following compound-I in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml * Compound-I: polypropyleneoxy -Polyethyleneoxy, di-succinate, sodium.

<H-1> Solution Ocein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml <S-1> solution Silver nitrate 309.2 g 28% ammonia solution equivalent Finish with water 1030.5 ml <H -2> Solution ossein gelatin 302.1g Potassium bromide 770.0g Potassium iodide 33.2g Finish with water 3776.8ml <S-2> solution Silver nitrate 1133.0g 28% ammonia solution equivalent Finish with water 3776.8ml Emulsion layer other than 10th layer For the silver iodobromide emulsion used for, the average grain size of seed crystal, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing H, flow rate, addition time, and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-
Mercaptotetrazole was added.

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

The structures of the compounds used in the above examples are shown below.

[0086]

[Chemical 1]

[0087]

[Chemical 2]

[0088]

[Chemical 3]

[0089]

[Chemical 4]

[0090]

[Chemical 5]

[0091]

[Chemical 6]

[0092]

[Chemical 7]

[0093]

[Chemical 8]

[0094]

[Chemical 9]

[0095]

[Chemical 10]

[0096]

[Chemical 11]

[0097]

[Chemical 12]

Example 2 A photosensitive material 2 was prepared in the same manner as in Example 1 except that the metal oxide of Example 1 was replaced with the oxide b shown in Table 1.

Example 3 A photosensitive material 3 was prepared in the same manner as in Example 1 except that the undercoating coating solution on the back layer side in Example 1 was replaced with the coating solution shown below.

1st layer acrylonitrile, vinylidene chloride and acrylic acid copolymer latex 0.025wt% 2nd layer acrylonitrile, vinylidene chloride and acrylic acid copolymer latex 0.025wt% vanadium silver pentoxide dope (b) 0.25wt% Nonionic activator (N-1) 0.01 wt% Third layer Ethyl acrylate / styrene / 2-aminoethyl methacrylate acrylate = 75/20/5 3 wt% Nonionic activator (N-1) 0.01 wt% Gelatin 0.6 The structural formulas of the N-1 compounds used in the second and third layers are shown below by wt%.

[0101]

[Chemical 13]

Example 4 A photosensitive material 4 was prepared in the same manner as in Example 3 except that the metal oxide of Example 3 was changed to the oxide b shown in Table 1.

Example 5 A light-sensitive material 5 was prepared in the same manner as in Example 4, except that the support in Example 4 was replaced with the support 2.

Example 6 A light-sensitive material 5 was prepared in the same manner as in Example 4 except that the support in Example 4 was replaced with the support 3.

Example 7 A light-sensitive material 7 was prepared in the same manner as in Example 4 except that the amount of metal oxide used in Example 4 was changed to that shown in Table 1.

Example 8 A light-sensitive material 8 was prepared in the same manner as in Example 4 except that the amount of metal oxide used in Example 4 was changed to that shown in Table 1.

Comparative Example 1 A light-sensitive material 9 was prepared in the same manner as in Example 1 except that the metal oxide of Example 1 was changed to oxide c.

Comparative Example 2 A light-sensitive material 10 was prepared in the same manner as in Example 4 except that the amount of metal oxide used in Example 4 was changed to the amounts shown in Table 1.

Comparative Example 3 A light-sensitive material 11 was prepared in the same manner as in Example 4 except that the amount of metal oxide used in Example 4 was changed to that shown in Table 1.

Next, the evaluation method and evaluation criteria of each sample (photosensitive material) are shown below.

<< Vulnerability >> The measurement was carried out in an atmosphere of −15 ° C. using the vulnerability tester shown in FIG.

One end of a film having a width of 35 mm and a length of 25 cm is sandwiched between the clip part 1 with the emulsion surface facing outward and bent by forming a loop at the part 2 and the film is taken out through the slit part 3 to the outside of the wedge. Hold part 4 by hand and pull the scale in parallel.

Since the film which breaks breaks inside the wedge, the broken length is read on a scale and this value is taken as the degree of weakness.
The following criteria were evaluated.

∘: less than 10 vulnerabilities ∘: more than or equal to 10 and less than 20 Δ: less than or equal to 20 and less than 40 ×: more than or equal to 40 or less than vulnerable is not preferable as a photographic support.

<< Transparency >> Haze The haze of the film after the development treatment is changed to Tu by Tokyo Denshoku Co., Ltd.
It was evaluated by rbidimeter Model T-260 ODA.

The photographic light-sensitive material is preferably 6% or less in practical use.

<< Surface Specific Resistance >> The sample after coating the emulsion was measured with a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd. under the conditions of an applied voltage of 100 V, 23 ° C. and 20% RH.

The evaluation results are shown in Table 1 below.

[0119]

[Table 1]

As is clear from Table 1, the examples of the present invention are superior to the comparative examples.

[0121]

The film according to the present invention has excellent effects on brittleness, transparency and antistatic property.

[Brief description of drawings]

FIG. 1 is a schematic view of a wedge-type brittleness tester used to measure the brittleness of the film of the present invention.

[Explanation of symbols]

 1 Clip part 2 Loop part 3 Slit part 4 Film edge part

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Saito 1 Konica Stock Company, Sakura Town, Hino City, Tokyo

Claims (2)

[Claims] 1. A film having at least one silver halide emulsion layer on at least one side of a layer made of copolyester and at least one layer containing vanadium pentoxide on at least one side. A film characterized in that the vanadium pentoxide is applied in an amount of 0.1 to 50 mg / m ² . 2. The film according to claim 1, wherein the film is a photographic support.