JP3409227B2 - Plastic film having antistatic layer and silver halide photographic material using the same as photographic support - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a plastic film having an antistatic layer and a support for a silver halide photographic light-sensitive material using the plastic film. Specifically, it relates to a plastic film having an antistatic layer containing a π-electron conductive polymer and a support for a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Generally, a plastic film is an insulator, and generation of undesired static electricity is a problem in various fields. For example, the silver halide photographic light-sensitive material (hereinafter sometimes abbreviated as light-sensitive material or photographic film) will be described. Especially, in the case of a photographic film having an insulating film support, an obstacle due to electrification during the manufacturing process, transportation in a camera, etc. Is likely to occur, and static electricity accumulated due to contact friction and peeling with the surface of the same kind or different material is discharged, and it cannot be detected unless the photographic light-sensitive material is exposed to light and developed. Cause defects. That is, the photographic light-sensitive material cannot be subjected to a destructive inspection before being shipped to the user and shipped, and if the user photographs and develops the defect to discover the defect, it becomes a defective product. Therefore, manufacturers have proposed many antistatic processing methods for plastic supports, which are insulators. The most proposed technology among these is to use ionic polymers, but the antistatic treatment with ionic polymers has the property that the charging performance depends on humidity, which means that static electricity may occur in low humidity conditions such as winter. It had a drawback in that As a method for solving this drawback, in recent years, a conductive antistatic technique using an electronic conductive substance such as metal oxide particles and π-electron conductive polymer has been proposed.

By the way, there are various restrictions in applying the antistatic technique to photographic light-sensitive materials. For example, it does not affect the sensitivity, fog, graininess, sharpness, color balance, etc. of the photographic light-sensitive material, does not adversely affect the adhesion resistance, does not accelerate fatigue of the processing liquid of the photographic light-sensitive material, Performances such as not delaying the drying, not contaminating the transport roller, and not lowering the adhesive strength between the constituent layers of the photographic light-sensitive material are required. A photographic light-sensitive material using a π-electron conductive polymer certainly has excellent antistatic performance at low humidity, but it is strongly colored and also has the above-mentioned performance as other photographic light-sensitive materials. It is in an unsatisfactory state and has not yet solved the above-mentioned problems.

[0004]

The problem of coloring due to the π-electron conductive polymer is essential in itself, and it is an important problem to solve it. It is known that it can be improved by reducing the thickness, but on the contrary, there is a contradictory problem that the antistatic performance is lowered. Further, when a binder is used in the antistatic layer, there is a problem that the antistatic performance cannot be maintained unless the π-electron conductive polymer is contained in the binder in a high concentration. There was a problem of being affected. In other words, there is a problem in that the amount of the binder can be reduced even if the binder is used and the π-electron conductive polymer is used in a small amount.

However, when a π-electron type conductive polymer is applied to a plastic film as an antistatic agent, there is a drawback that workability is poor. That is, when the π-electron conductive polymer is used as a working liquid in the form of a solution, the polymer is often difficult to be a solution and it is often difficult to select a solvent. Therefore, when preparing an antistatic processing liquid of a π-electron conductive polymer, how to improve the processability in the state of dispersion of fine particles, and how to form a film that exhibits sufficient antistatic performance, and in a transport system are sufficient. There were some problems as to whether a film capable of withstanding the strength could be made. The present inventors have speculated that this problem may be caused by irregular particle sizes.

A first object of the present invention is to provide a plastic film having an antistatic layer having excellent antistatic performance by aligning π-electron conductive polymer particles. The second object of the present invention is to provide a silver halide photographic light-sensitive material having the plastic film as a photographic support.

[0007]

Means for Solving the Problems The present inventors have made the average particle size of a π-electron conductive polymer dispersed in a solid state 0.1 to 0.5.
A plastic film with excellent processability and film-forming properties, strong film strength, and excellent antistatic performance, and a photographic support for the same, by making the particle size μm and the fluctuation of the particle size 50% or less. The silver halide photographic light-sensitive material used could be obtained, and the above-mentioned problems could be achieved.

The present invention will be described in detail below.

In the π-electron conductive polymer according to the present invention, a conjugated system in which a double bond or a triple bond connecting a carbon atom and a carbon atom or a hetero atom is alternately long and continuous with a single bond is used as a molecular skeleton. It is a conjugated polymer. Examples of these conjugated polymers include 1) aliphatic conjugated systems: polymers in which carbon-carbon conjugated systems such as polyacetylene are alternately long, and 2) aromatic conjugated systems: aromatic hydrocarbons such as poly (paraphenylene). A polymer in which conjugation has been developed in which a long bond is formed, 3) a heterocyclic conjugated system: a polymer in which a conjugated system is developed by binding a heterocyclic compound such as polypyrrole or polythiophene, 4) a hetero atom-containing conjugated system: a fat such as polyaniline 5) Mixed type conjugated system: conjugated type polymer having a structure in which constituent units of the above conjugated type such as poly (phenylene vinylene) are alternately bonded, 6) polymer Chain-type conjugated system: A conjugated system having a plurality of conjugated chains in the molecule and having a structure similar to an aromatic conjugated system, 7) Metal phthalocyanine system: Metal lid Cyanine or a polymer in which these molecules are bound to each other by a hetero atom or a conjugated system, 8) Conductive complex: a polymer in which the conjugated polymer chain is graft-copolymerized with a saturated polymer, and the conjugated polymer is polymerized in a saturated polymer. The complex etc. which are obtained by doing are mentioned.

When the above-mentioned π-electron-type conductive polymers are shown below as a polymer group, 1) is polyacetylene, poly (1,6-heptadiene), etc., 2) is polyparaphenylene, polynaphthalene, poly. Anthracene, etc. 3) Polypyrrole and its derivatives, Polyfuran and its derivatives, Polythiophene and its derivatives, Polyisothionaphthene and its derivatives, Polyselenophene and its derivatives, etc. 4) Polyaniline and its derivatives, etc. Poly (paraphenylene sulfide) and its derivatives,
Poly (paraphenylene oxide) and its derivatives, poly (paraphenylene selenide) and its derivatives, and in aliphatic systems, poly (vinylene sulfide), poly (vinylene oxide), poly (vinylene selenide), etc. (Paraphenylene vinylene) and its derivatives, poly (pyrrole vinylene) and its derivatives, poly (thiophenvinylene) and its derivatives, poly (furan vinylene) and its derivatives, poly (2,2'-thienyl pyrrole) and its derivatives, etc. , 6) is polyperinaphthalene, 7) is metal phthalocyanine, and 8) is 3) polythiophene (including derivative), polypyrrole (including derivative), 4) polyaniline (including derivative), etc. To
Moreover, π of a polymer having poly (paraphenylene vinylene) (including its derivative), poly (thiophenvinylene) (including its derivative) or the like in 5) in a side chain through a connecting group.
Examples thereof include electronically conductive polymer composites.

Among the above, the heterocyclic conjugated system of 3), 4)
The heteroatom-containing conjugated system of 5), the mixed conjugated system of 5), and the electroconductive composite system of 6) are easy to obtain high electroconductivity, and are preferable as the electroconductive polymer of the present invention.

Furthermore, among these, the following general formula ASP
Polymers having repeating units represented by (I), ASP (II), ASP (III), and ASP (IV) are particularly preferred in the present invention.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017] Here, in the formula, X _{is> N-R X, -S -} , -
O -, - Se- _{represents, R 1, R 2, R} 3, R 4, R 5,
_{R 6, R 7, R 8} , R 9, R 10, R 11, R 12, R 13, R 14,
R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an allyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, a carboxyl group, an alkyl group. It represents a carboxyl group or a sulfamide group. R _X represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyloxy group, an allyl group, an aryl group, an aralkyl group, an acyl group, an alkylcarboxyl group or an alkylsulfoamide group, and a hydrogen atom is particularly preferable. Further, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R _X may be the same or different. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , R ₉ and R ₁₀ , R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ ,
R ₁₅ and R ₁₆ and R ₁₇ and R ₁₈ may be bonded to each other to form a ring.

These R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
_{7, R 8, R 9,} R 10, R 11, R 12, R 13, R 14, R 15,
R ₁₆ , R ₁₇ and R ₁₈ and R _X may each have a substituent, and as the substituent, an alkyl group, an allyl group, an aryl group, a halogen atom, a hydroxy group, an alkoxy group, an amide group, a nitro group At least one group selected from a cyano group, an acyl group, a carboxyl group, and an alkylcarboxyl group.

The general formula ASP (I) has the above 3) and 5), and the general formula ASP (II) has the above 4).
(III) contains the above 4), and general formula ASP (IV) contains the above 5).

The π-electron conductive polymer of the present invention can be polymerized by a conventional method. The synthesis method is a direct synthesis method in which a polymer having a conjugated skeleton is directly synthesized by polymerizing a monomer, and a soluble precursor polymer is synthesized by polymerizing a monomer, and a conjugated system is formed by elimination reaction or addition reaction. It can be roughly divided into an indirect synthesis method to form, but it is difficult to form a long conjugated system in the indirect synthesis method, and a direct synthesis method is mainly used.

In the direct synthesis method, a chain polymerization method such as addition polymerization, ring-opening polymerization and cyclization polymerization, or a sequential polymerization method such as polycondensation can be used. This method includes a chemical oxidative polymerization method and an electrolytic oxidative polymerization method.

Regarding the method for polymerizing the π-electron type conductive polymer of the present invention, 57 of “Conductive Polymer”, edited by Naoya Ogata, referred to above.
~ Page 93 for more details. And more specifically,
JP-A-2-255770, JP-A-2-252726, J, Che
m.Soc.Chem.Commun., 1983, p.854, J.Polym.Sci.Poly
m. Lett. ed., vol. 18, p. 9 (1980), J. Chem. Soc. Chem. Comm.
un.1986, 1348, Polymer 27, 455 (1986), Syn
thetic Metals, 26, 383 (1988), Polymer Commu
n., 28, 229 (1987) and the like, and the π-electron conductive polymer of the present invention can be synthesized by these.

In the above chemical oxidative polymerization method, the monomer is dissolved or dispersed in water or an organic solvent, and the oxidant solution is slowly added in a temperature range of -30 to 70 ° C, preferably -10 to 5 ° C. A polymer that can be easily processed later is obtained by dropping and reacting.

In the electrolytic oxidative polymerization method, the monomer and the conductive salt are dissolved or dispersed in water or an organic solvent to immerse the positive and negative electrodes, and the temperature is -30 to 90 ° C, preferably -10 to 90 ° C. 5
At constant temperature method, constant voltage method, constant potential method or constant current method.

As catalysts used in the chemical oxidative polymerization method, chlorides such as FeCl ₃ and CuCl ₂ , sulfates such as Fe ₂ (SO ₄ ) ₃ and CuSO ₄ , K ₂ S ₂ O ₈ and (NH _{4 ) 2 S 2 0 8, H} 2 0 2 peroxides such as, quinones benzoquinone, halogens such as I _2, Br _2, potassium ferricyanide, and the like. The amount of catalyst varies depending on the monomer, but it can be used in a molar ratio of 0.01 to 10.

As the electrode material used in the electrolytic oxidation polymerization method, metal electrodes such as Au, Pt, Ni, Cu and Sn, carbon electrodes, Sn
O _2, In ₂ 0 ₃ or the like of the metal oxide electrode, ITO glass (indium - tin oxide coated glass), and the like.

The conductive salt used in the electrolytic oxidation polymerization method includes alkali metal cations such as Li ⁺ , Na ⁺ and K ⁺ , N
O ^+, NO ^2+, also Et ₄ N ^+, and _{^{Bu 4 N +, Bu 2 P}} + such onium _{^{cation, BF 4 -, AsF 4 -}} , AsF 6 -, SbF 6 -, SbCl 4 -, PF 6 ^- , C
_{^{lO 4 -, AlF 4 -,}} AlF 6 -, NiF 4 2-, ZrF 6 2-, TiF 6 2-, HS
O ₄ ⁻ , SO ₄ ²⁻ , Cl ⁻ , Br ⁻ , F ⁻ , I ⁻ etc. negative ions and salts thereof, CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , CF ₃ SO ₃ ^-, sulfonate anion and their salts, such as polystyrene sulfonic acid, HCOO
Examples thereof include salts such as Li and sodium polyacrylate, chlorides such as FeCl ₃ , and organic amine salts such as pyridine hydrochloride.

Solvents that can be used in the chemical oxidative polymerization method and the electrolytic oxidative polymerization method include acetonitrile, benzonitrile, methylene chloride, dimethylsulfate, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide and sulfolane. , Formamide, dimethoxyethane, propylene carbonate, dioxane, methanol, ethanol, γ-butyl lactone, nitrobenzene, tetrahydrofuran, nitromethane and the like,
Water or a mixture of both can be mentioned.

In addition, during chemical oxidative polymerization or electrolytic oxidative polymerization, inorganic acids such as hydrochloric acid and sulfuric acid, CH ₃ C ₆ H ₄ SO ₃ H, CF ₃ SO ₃ H, sulfonic acids such as polystyrene sulfonic acid, and formic acid. Alternatively, a conductive compound such as carboxylic acid such as acetic acid or polyacrylic acid may be added to perform polymerization.

When the π-electron conductive polymer of the present invention is dispersed and polymerized, cations, anions, nonions,
Polymers such as betaine and surfactants can be used. For example, polyvinyl alcohol, polyethylene oxide, polypropylene oxide, hydroxycellulose, carboxycellulose, methylcellulose, dextrin, polyvinylpyrrolidone, styrene and sodium styrenesulfonate, acrylic acid and its salts, acrylamide or sodium 2-acrylamido-2-methylpropanesulfonate. Copolymer with etc., polyacrylamide, polyacrylic acid and its sodium salt, gelatin,
Examples thereof include casein, sodium laurate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium laurylsulfonate, sulfosuccinic acid ester salt, trimethylammonium chloride, polyethylene glycol, sorbitan fatty acid ester and the like. The amount of dispersant used is 1 to 300% by weight, preferably 5 to 200% by weight, based on the monomers. When a surfactant is used, it is 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the monomer. The polymer obtained by the above-mentioned polymerization method includes those that precipitate at the bottom of the reaction vessel, those that are in a suspended state, that are in the form of latex, those that are transparent solutions, and those that are deposited as a film on the electrode. Although various methods are available, it is preferable to use it after purification by dialysis, ultrafiltration, washing and the like. It is preferable to use the solution after it is precipitated.

The π-electron conductive polymer of the present invention is used with an average particle size of 0.1 to 0.5 μm and a coefficient of variation of 50% or less. As a method for controlling the dispersion as much as possible in the average particle diameter and the coefficient of variation of the particle diameter of the present invention as described above, a ball mill, a vibration mill, a planetary ball mill, a sand mill, a colloid mill or a jet mill in the presence of a dispersant is used. Grind for the time necessary for mechanical crushing, align the mesh so that it can be dispersed in fine particles, and crush to an average particle size of 0.05 to 1 μm, preferably 0.1 to 0.5 μm, and then surfactant, water-soluble polymer, etc. It is preferable to add the dispersant of (1) to water to disperse the particles. As these dispersants, the same dispersants as those used in the above synthesis can be used. After crushing, it is necessary to further adjust the average particle size of the particles and the coefficient of variation of the particle size by centrifugation, pressure filtration, polytron, dissolver or the like. If the pulverization time is short, the particle size and the coefficient of variation are unlikely to reach the values required by the present invention even after the subsequent treatment.

When the π-electron conductive polymer of the present invention is in the form of a latex or a latex, the dispersant is not necessary because it already contains the dispersant.
You may add as needed.

The coefficient of variation of the π-electron conductive polymer of the present invention is a value expressed by S / d, where d is the average particle size and S is the standard deviation of the particle size. The average particle diameter and standard deviation can be obtained by measuring with DLS-700 manufactured by Otsuka Electronics Co., Ltd.

A solvent (for example, water, ethanol, etc.) may coexist at the time of dispersion. When the π-electron conductive polymer is dissolved in a solvent, it may be precipitated as fine crystals by adding a poor solvent for the polymer after forming a solution.

As the dopant used in the present invention,
Halogen molecules (eg Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IB
r, IF), Lewis acid (eg, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , B)
Cl ₃ , BBr ₃ , SO ₃ ), protic acid (eg HF, HCl, HNO)
₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, various organic acids, amino acids, etc., transition metal compounds (eg FeC)
l ₃ , FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaC
l ₅ , MoF ₅ , MoCl ₅ , WF ₆ , WCl ₆ , LnCl ₃ (Ln is La, Ce, P
r, Nd, lanthanides such as Sm)), an electrolyte anion ^{(e.g., Cl -, Br -, I} -, ClO 4 -, PF 6 -, AsF 6 -, Sb
^{_{F 6 -, BF 4 -,}} CF 3 SO 3 -, CF 3 CO 2 -, CH 3 SO 3 -, CH 3 C 6 H 5 S
O ₃ ^-), a polymer electrolyte anions (e.g. polyvinyl sulfate, polystyrene sulfonate, poly (p- vinylbenzyl sulfonic acid), polyacrylic acid, polyethylene sulfonic acid, polyvinyl sulfonic acid, polyphosphoric acid, polyaspartic acid) or the like, other O ₂ , XeOF ₄ , (NO ₂ ⁺ ) (SbF ₆ ),
^{_{(NO 2 +) (SbCL 6}} -), (NO 2 +) (BF 4 -), FSO 2 OOSO 2 F,
_{AgClO 4, H 2 IrCl 6,} La (NO 3) 3 · 6H 2 O or the like can be mentioned, but not limited thereto. I ₂ , Br ₂ , HC
l, H ₂ SO ₄ , AsF ₅ , SbF ₅ , KBF ₄ , LiBF ₄ , (C ₂ H ₅ ) ₄ NBF ₄ ,
FeCl ₃ , LiClO ₄ , CF ₃ SO ₃ Li, CF ₃ SO ₃ Na, CF ₃ SO ₃ H, LiBr,
Paratoluene sulfonic acid and polystyrene sulfonic acid are preferably used.

The method of doping π-electron-type conductivity of the present invention is mainly a chemical doping method in which a dopant and a π-electron-type conductive polymer are reacted in a solution system, but an electrochemical doping method is also available. Good.

As the doping method, for example, the doping can be performed by allowing a dopant to exist in the polymerization field of the π-electron conductive polymer. A dopant may be added at the time of preparing the antistatic coating solution, but doping at the polymerization site is preferable. In addition, in the case of electrochemical polymerization, the film-shaped polymer deposited may be immersed in the dopant solution, or the film may be molded and then doped.

The dopant doped in the π-electron conductive polymer of the present invention is preferably present in an amount of 1 mol% or more per repeating unit of the π-electron conductive polymer, and more stable when it is 10 mol% or more. A conductivity level can be obtained, which is particularly preferable.

Among the catalysts, conductive compounds, electrolytes and acidic compounds shown in the above chemical oxidative polymerization method or electrolytic oxidative polymerization method, there are also the same compounds as the dopant of the present invention, and these compounds are used during the synthesis. Needless to say, the π-electron-type conductive polymer may be doped to serve as a dopant, and is within the range of doping according to the present invention.

Exemplary compounds in which the π-electron conductive polymer of the present invention and a dopant are combined are shown below, but the invention is not limited thereto.

[0041]

[Chemical 5]

[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

[Chemical 8]

[0045]

[Chemical 9]

[0046]

[Chemical 10]

[0047]

[Chemical 11]

[0048]

[Chemical 12]

The π-electron conductive polymer of the present invention is used as a coating composition in a dispersion state. When the content thereof is applied as an antistatic layer, in order to enhance conductivity,
It is preferably 0.5 to 50% by weight, particularly preferably 1 to 20% by weight in the composition. The solvent used in the coating composition may be water or an organic solvent, but the use of water is preferred from the economical and environmental viewpoints. Acetone as the organic solvent,
Methanol, methanol, isopropanol, methyl ethyl ketone, acetonitrile, ethyl acetate, formamide, acetamide, dimethylformamide, dioxane and the like are used, but not limited thereto.

The number of average repeating units of the π-electron conductive polymer in the present invention is suitably 3 to 100,000, preferably 5 to 10,000, more preferably 10 to 3,000.
Is.

(Synthesis Example) An example of the synthesis method of the π-electron conductive polymer is shown below, but the synthesis method is not limited thereto.

1-1) Synthesis of polypyrrole [ASP (I)
-1] 8 g of iodine was added to 1000 ml of deionized water, and then pyrrole was added.
182 mol is added, and the reaction container is left for 50 hours in a cool and dark place. A black substance precipitates on the bottom of the reaction vessel. This black reaction product was washed with a large amount of methanol, then washed with acetonitrile, carbon tetrachloride, and 95% ethanol in this order, taken out, immersed in a large amount of absolute ethanol for 24 hours, taken out, and taken out with anhydrous ethanol to give a black substance. Was added, the mixture was boiled for 1 hour for washing, this was repeated several times, and then vacuum dried to obtain 4.8 g of polypyrrole. This product had an average degree of polymerization of about 1,000 as determined by elemental analysis and NMR.

1-2) Poly (3,4-dimethoxypyrrole)
Synthesis of [ASP (I) -6] 3,4-dimethoxypyrrole (12 g), (C ₄ H ₉ ) ₄ NBF ₄ ( ₄ g) and acetonitrile (200 ml) were taken, and this solution was stirred at room temperature under a nitrogen atmosphere and distilled water was added to the solution. 70g dissolved in 30ml
The FeCl ₃ · 6H ₂ O was added dropwise over 30 minutes. Heat was generated with dropping, and a solid substance was produced. After further stirring for 2 hours, the obtained solid substance was collected by filtration and dried to obtain poly (3,4-dimethoxypyrrole). This product had an average degree of polymerization of 43 from the results of elemental analysis and NMR.

1-3) ASP was similarly carried out by the above two synthetic methods.
(I) -4, 5, 7, 8, 9 and 10 were respectively synthesized. The respective average degrees of polymerization are shown in Chemical Formulas 5 and 6 above.

2-1) Synthesis of polythiophene [ASP
(I) -2] To 300 ml of nitrobenzene, 0.6 mol of iron trioxide was added, and 0.1 mol of 2-chlorothiophene was added dropwise over 45 minutes at 100 ° C under a nitrogen stream. After dropping, the mixture was stirred at 60 ° C. for 5.5 hours, and then the nitrobenzene solution was concentrated. To this, 500 ml of ethyl acetate was added, and the product was extracted by heating and purified using a Sephadex column to obtain 6 g of polythiophene. This is elemental analysis and NM
From R, the average degree of polymerization was 1,200.

2-2) Synthesis of poly-3,4-diethoxythiophene [ASP (I) -16] 30 g of polystyrenesulfonic acid (number average molecular weight 3,700)
It was dissolved in 1.5 liters of water, and 72 mmol of K ₂ S ₂ O ₈ , 0.375 mmol of Fe ₂ (SO ₄ ) ₃ and 210 mmol of 3,4-diethoxythiophene were added thereto under a nitrogen stream, and the temperature was adjusted to 20 ° C. The mixture was reacted with stirring for 24 hours. To this was further added 750 ml of water, and strongly acidic and weakly basic ion exchange resins (Amberlite (registered trademark) IR120 and IRA400, respectively, were added to the mixture, and the mixture was mixed at room temperature for 8 hours for desalting. Then, the ion-exchange resin was filtered off to obtain a dispersion liquid of poly-3,4-diethoxythiophene.The polymer obtained by concentration and purification was found to have an average degree of polymerization of 40 by elemental analysis and NMR.

2-3) Synthesis of poly-3,4-diethoxythiophene 1.5 mol of iron trichloride was added to 1 liter of nitrobenzene and heated at 100 ° C. under a nitrogen stream to give 2-chloro-3,4-diethoxythiophene.
5 mol was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred at 60 ° C. for 6 hours, the nitrobenzene solution was concentrated, 500 ml of ethyl acetate was added, and the mixture was extracted by heating and purified by a Sephadec column to obtain 70 g of poly-3,4-dimethoxythiophene.
This product had an average degree of polymerization of 40 by elemental analysis and NMR.

2-4) ASP was similarly carried out by the above-mentioned synthesis method.
(I) -11, 12, 13, 14, and 15 were obtained. The average degree of polymerization is described in Chemical Formulas 6 and 7 above.

2-5) As for ASP (I) -3 and 24, 2-chlorofuran and 2-chlorofuran are used as monomers, respectively.
It can be similarly obtained by the above-mentioned synthetic method using -3,4-dimethoxyselenophene. The average degree of polymerization and the dopant are described in Chemical formulas 5 and 9 above.

2-6) For ASP (I) -25 and 26, 2,2'-thienylpyrrole and 2,5-di (2-
It can be similarly synthesized using thienyl) -pyrrole. The average degree of polymerization and the dopant are described in Chemical formula 9 above.

3-1) Synthesis of Polythianaphthene [ASP
(I) -17] Dextran 5 g, distilled water 100 ml, and isothianaphthene dissolved in methylene chloride 10 ml with stirring under a nitrogen atmosphere.
10 g was added to obtain a suspension. Distilled water in this suspension at room temperature
20 g FeCl ₃ .6H ₂ O dissolved in 30 ml was added dropwise over 30 minutes. Heat was generated with dropping, and polymerization proceeded. After further stirring for 2 hours, dialysis was performed to obtain an aqueous dispersion of polyisothianaphthene. After 3 months, this aqueous dispersion did not show any precipitation and no change in particle size was observed. The solid content as polyisothianaphthene was 8.5 g.

3-2) Poly (5-dodecylbenzo [c] thiophene) [ASP (I) -19] 5-dodecylbenzo [c] thiophene 3 g and tetramethylammonium chloride 2 g dissolved in acetonitrile 150 ml were reacted. Electrolyte solution, using ITO plate (surface resistance value 10 / □) for working electrode, Pt plate for counter electrode, Li / Li ⁺ for reference electrode, electrochemical at constant voltage of 2.5V for 30 minutes When polymerized, a film of poly (5-dodecylbenzo [c] thiophene) was formed on the working electrode. This film is soluble in tetrahydrofuran, toluene, xylene, propylene carbonate, methylene chloride, dimethylformamide, N-methylpyrrolidone, N, N'-dimethylacetamide and has processability. This product had an average degree of polymerization of 83 by elemental analysis and NMR. This film was immersed in a 5 wt% H ₂ SO ₄ aqueous solution for doping.

3-3) Similarly to ASP by the above synthesis method
(I) -18 and 20 were obtained. The average degree of polymerization and the dopant are described in Chemical formula 8 above.

4-1) Synthesis of polyaniline 1 [ASP (I
I) -1] Distilled and purified aniline 0.15 mol and 1.33 mol / ml hydrochloric acid
After adding 150 ml and keeping it at -5 ° C, 0.07 mol of ammonium persulfate dissolved in 30 ml of distilled water was added dropwise to this while stirring for 1 hour, and when stirring was continued for 12 hours later, the polymer gradually precipitated. Will occur. The precipitated polymer is filtered off, washed with distilled water, continued to be washed until the pH becomes 6 or more, and then repeatedly washed with methanol until the solution becomes transparent. 5 g of polyaniline was obtained. This product had an average degree of polymerization of 83 according to elemental analysis and NMR.

4-2) Synthesis of polyaniline 2 0.2 mol of distilled aniline, 0.7 mol of LiClO ₄ and 1,000 ml of acetonitrile were stirred while using a Pt plate for both the positive and negative electrodes, and a constant voltage method (3 V, ² mA / cm ² ) For 1 hour to obtain a polymer deposit on the negative electrode. Then, the polymer precipitate was heated and extracted with methyl ethyl ketone to obtain 18 g of polyaniline. This product had an average degree of polymerization of 110 according to elemental analysis and NMR.

4-3) ASP (II) -using the above method
2,3,4,5,6,7,8,9 and 10 were synthesized. The average degree of polymerization and the dopant of each of these are described in Chemical formulas 10 and 11 above. 5-1) Synthesis of poly (paraphenylene vinylene) [ASP
(IV) -1] 0.1 mol of p-xylene dichloride was dissolved in 200 ml of acetone, 0.24 mol of diethyl sulfide was added dropwise at -5 ° C over 1 hour, and after 3 hours at room temperature, 0.12 mol of sodium hydroxide aqueous solution was added. 100 ml of the solution was added dropwise over 30 minutes to initiate the polymerization, and the reaction was advanced while adding 100 ml of water to give a viscous solution. The reaction solution was cast on a stainless plate to form a film, water was heated to evaporate, the film was peeled from the stainless plate and heated in an oven at 280 ° C. for 30 minutes to obtain a transparent film. This film was washed in water to remove unreacted substances and sulfur compounds, and dried. As a result of measuring this by elemental analysis and NMR, it was poly (paraphenylene vinylene) and the average degree of polymerization was 200. Doping was performed by immersing this film in a 5 wt% polystyrene sulfonic acid solution for 3 hours.

5-2) Synthesis of poly (3,6-dimethoxyparaphenylenevinylene) [ASP (IV) -2] 1,4 dichloromethyl-3,6-dimethoxybenzene 0.1 mol 2
Dissolve in 00 ml acetone and add diethyl sulfide at -5 ℃.
0.25 mol was added dropwise over 1 hour, and after 3 hours at room temperature, a water-methanol mixture containing 0.12 mol of sodium hydroxide (50/50 volume fraction) was added to carry out a polymerization reaction, and after 3 hours, the reaction was completed. Continue neutralization and add 100 ml of methanol.
In addition, after continuing the reaction, precipitate in a large amount of water to wash, dry, dissolve in tetrahydrofuran, cast on a stainless steel plate and dry, peel from the plate, 250 ° C
After heating for 30 minutes in the oven, a transparent film was obtained. This film is poly (3,
After confirming that it was 6-dimethoxyparaphenylene vinylene), the average polymerization degree was 55.

5-3) ASP (IV) -3 and 4 were similarly synthesized by either of the above two methods. The average degree of polymerization and the dopant are described in Chemical formula 12 above.

Next, the average particle size of the above-mentioned composition of the present invention is 0.
A method for producing a dispersion for achieving a coefficient of variation of 1 to 0.5 μm and 50% or less will be described.

(A): 30 ml of water and the surfactant Triton X
50 ml of a 10% by weight aqueous solution of -200 (trade name of Union-Carbide Co., Ltd.) was mixed with 8 g of ASP (I) -6, and low-alkali type glass beads (trade name: Hibee, manufactured by OHARA).
It was dispersed in a dynomyl (Willya Bachofenag, horizontal sand mill) for 30 hours. After the dispersion is complete, remove the bubbles and filter with gauze to remove the glass beads.
(I) -6- (a) was obtained.

(B): 8,000r of the above dispersion liquid (a)
After centrifugation at pm to remove the precipitate, ASP (I) -6-
(B) was obtained.

(C): The above dispersion liquid (a) was dispersed with Polytron at 5,000 rpm for 5 minutes to prepare ASP (I) -6.
-(C) was obtained.

(D): The above dispersion liquid (a) was filtered under pressure with a 3 μm glass filter to obtain a filtrate ASP (I)-
6- (d) was obtained.

In the same manner, various π-electron conductive polymer dispersions were prepared in the same manner as in (a) to (d), and (a) to (d) were added after the ASP number. The method for preparing the comparative dispersion liquid is the same as that in (a) except that the dispersion time of 30 hours is changed to 15 hours, but is as follows.

(W): 30 ml of water and Triton X, a surfactant
50 ml of a 10% by weight aqueous solution of -200 (trade name of Union-Carbide Co., Ltd.) was mixed with 8 g of ASP (I) -6, and low-alkali type glass beads (trade name: Hibee, manufactured by OHARA).
It was dispersed for 15 hours with Dynomile. After the dispersion is complete, remove the bubbles and filter with gauze to remove the glass beads,
ASP (I) -6- (w) was obtained.

(X): The above dispersion liquid (w) was further added to 8,000r.
After centrifugation at pm to remove the precipitate, ASP (I) -6-
(X) was obtained.

(Y): The above dispersion liquid (w) was dispersed with a polytron at 5,000 rpm for 5 minutes to prepare ASP (I) -6.
-(Y) was obtained.

(Z): The above dispersion liquid (w) was filtered under pressure through a 3 μm glass filter to obtain a filtrate ASP (I)-
6- (z) was obtained.

Similarly, various comparative π-electron type conductive polymer dispersions were prepared by the same method (w) to (z), and (w) to (z) were added after the ASP number.

The average particle size and the coefficient of variation of the particle size of the produced π-electron conductive polymer dispersion are shown in the table of each example.

The antistatic coating liquid containing the π-electron type conductive polymer of the present invention may contain a binder useful for forming a layer, if necessary. Examples of the binder include the same as the polymer used when the above-mentioned dispersion and polymerization are performed. That is, as the binder polymer, polyvinyl alcohol, polyethylene oxide, polypropylene oxide, hydroxycellulose, carboxycellulose, methylcellulose, dextrin, polyvinylpyrrolidone, styrene or alkyl acrylate and sodium styrenesulfonate, acrylic acid and its salts, acrylamide or 2-acrylamide. 2-Copolymers with sodium 2-methylpropanesulfonate and the like, polyacrylamide, polyacrylic acid and sodium, aqueous copolyesters, gelatin, casein and the like are useful, and among them, gelatin is preferably used. As a raw material of gelatin, there are pigskin, calfskin, ossein and the like, and as a treatment method of gelatin, there are acid treatment and alkali treatment (lime soaking treatment).
As the type of gelatin, acid-treated pigskin gelatin,
There are acid-treated ossein gelatin, alkali-treated calfskin gelatin, alkali-treated ossein gelatin and the like, all of which can be used as the binder of the antistatic coating solution of the present invention. Of these, alkali-treated gelatin contains a large amount of calcium ions, and therefore it is preferable to use calcium ion exchange resin or the like to decalcify ions if necessary. Ion exchange treatment uses gelatin solution 30 ~
Preference is given to carrying out at a temperature of 60 ° C.

The amount of the binder in the antistatic coating liquid containing the π-electron conductive polymer of the present invention is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the composition. %.

The water-insoluble polymer may be contained in the antistatic coating liquid containing the π-electron type conductive polymer of the present invention. As the monomer component of the water-insoluble polymer, alkyl acrylate or alkyl methacrylate (alkyl: methyl, ethyl, n- or iso-propyl,
n-, sec-, and ter-butyl, cyclohexyl, 2-ethylhexyl, hydroxyethyl, glycidyl, etc.), styrene, acrylonitrile, butadiene, isoprene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylamide, etc.) and / or other Examples of the homo- or copolymer latex according to the combination of, a urethane resin dispersion liquid, a polyethylene resin dispersion liquid, and the like. Above all, it is preferable to add a latex polymer to the composition, and it is particularly preferable to use gelatin as a binder. These water-insoluble polymers are preferably contained in the antistatic coating liquid in an amount of 0.5 to 20% by weight.

Various other additives can be added to the antistatic coating liquid containing the π-electron type conductive polymer of the present invention. For example, a hardener, a surface tension adjusting agent, a matting agent and the like can be mentioned.

Particularly when gelatin is used as the binder, it is important to insolubilize the antistatic gelatin layer after coating so that the antistatic layer is not dissolved or eluted during the processing such as development. As a result, in addition to insolubility and non-elution, the antistatic layer reduces the amount of water absorbed during development processing, speeding up drying,
The processing speed can be increased. Insolubilization of gelatin is achieved by adding a hardener to gelatin to the composition. As a hardener,
Epoxy-based, aldehyde-based, ethyleneimine-based, active ester-based, active ethylene-based and the like can be mentioned, which can be usefully used, but are not limited to the following compounds.

[0086]

[Chemical 13]

[0087]

[Chemical 14]

<Antistatic Plastic Film>
The antistatic plastic film of the present invention can be obtained by coating the plastic film with the π-electron conductive polymer antistatic coating liquid of the present invention.

<Plastic Film> The plastic film according to the present invention includes polyethylene terephthalate, polyethylene naphthalate, modified polyester containing metal sulfoaromatic dicarboxylic acid, polyester containing metal sulfoaromatic dicarboxylic acid and polyethylene terephthalate and / or polyethylene naphthalate. Laminated structure with polyester, polycarbonate, polyamide, polyimide, polyphenyl sulfone, polyphenyl ether, polystyrene, cellulose triacetate, polyethylene, polypropylene, polyethylene laminated film and the like film, but is not limited to these . Among them, as a plastic film useful for a photographic support, polyethylene terephthalate, polyethylene naphthalate, modified polyester containing metal sulfoaromatic dicarboxylic acid, laminate of polyester containing metal sulfoaromatic dicarboxylic acid and polyethylene terephthalate and / or polyethylene naphthalate Structure polyester, polycarbonate, polystyrene especially syndiotactic polystyrene, cellulose triacetate,
Films such as polyethylene laminated paper are preferred.

Cellulose triacetate film is mainly used for color photographic film and is widely used. The cellulose triacetate film was prepared by dissolving cellulose triacetate as a raw material in methylene chloride to form a viscous solution, which was extruded from a die to a predetermined thickness on an endless stainless steel belt and dried on a belt, and the belt made one round. By the way, it is peeled from the belt, further heated from both sides, and the solvent is removed. The polycarbonate film can be produced in the same manner as the cellulose triacetate, but a commercially available polycarbonate film can be used in the present invention.

Polyethylene terephthalate film is mainly used for printing photographic film or medical photographic film (also called X-ray film), but is also used for color photographic film. Recently, proposals have been made to apply polyethylene naphthalate film, modified polyester film, polycarbonate film, syndiotactic polystyrene and the like to new photographic films.

Polyethylene terephthalate film and polyethylene naphthalate, especially polyethylene-2,6-naphthalate can be prepared by a conventional method of polyester, but since they are generally commercially available, they can be used as the plastic film according to the present invention. I can.

The modified polyester film can be used to form resin chips and films by a conventional method as in the case of polyethylene terephthalate.

Further, the laminated polyester film comprises the modified polyester, polyethylene terephthalate and / or
Alternatively, a film obtained by mainly combining polyethylene naphthalate in three or more layers can be prepared from each raw material from an extrusion die for lamination in the same manner as a normal polyethylene phthalate.

The laminated polyester film was developed by the applicant of the present invention as a film having less curling tendency.

The modified polyester and the laminated polyester film will be described below as to how to make these films.

The metal sulfoaromatic dicarboxylic acid modified polyester constituting at least one layer of the laminated film preferably has polyethylene terephthalate or polyethylene naphthalate as a main constituent component of the modified polyester. That is, it is a polymer having many repeating units containing terephthalic acid and ethylene glycol as main constituents, and a polymer having many repeating units containing naphthalenedicarboxylic acid and ethylene glycol as main constituents. The naphthalene dicarboxylic acid is preferably naphthalene-2,6-dicarboxylic acid.
Having a large number of repeating units means that the repeating unit is 70 mol% or more, preferably 85 mol% or more, and particularly preferably 90 mol% or more.
It means that there is more than mol%.

The remaining modified portion contains terephthalic acid, 2,6-naphthalenedicarboxylic acid, another naphthalenedicarboxylic acid, an aromatic dicarboxylic acid having a metal sulfonate group, an aromatic dicarboxylic acid such as isophthalic acid, as an acid component. Aliphatic dicarboxylic acids such as adipic acid and sebacic acid, free acids such as polyether dicarboxylic acid such as polyethylene oxide dicarboxylic acid and polypropylene oxide dicarboxylic acid, diesters of these with C _{1 to} C ₄ alcohols,
Alternatively, dihalf esters with C _{2 to} C ₁₀ glycols, and glycol components such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, p-xylidene glycol, 1,4-cyclohexanedimethanol and the like. And polyolefin oxide glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polyethylene oxide-polypropylene oxide copolymer glycol and the like.

As the metal sulfoaromatic dicarboxylic acid as the modifying component of the modified polyester, isophthalic acid containing a metal sulfonate group is preferable, the metal ion is an alkali metal such as sodium, potassium, lithium or cesium, and sodium is preferable. Specifically, 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid or their methyl esters, ethylene glycol half esters, other The glycol half ester represented by 15 and the like can be mentioned, but preferably 5-sodium sulfoisophthalic acid or its methyl ester or ethylene glycol ester is also used. It may be contained in a proportion of 2 to 10 mol% based on the total ester bonds of the modified polyester of aromatic dicarboxylic acid having a metal sulfonate group. It is preferably 2 to 7 mol%, particularly preferably 3 to 6
Mol%.

[0100]

[Chemical 15]

The polyalkylene glycols useful as a modifying component of the modified polyester are preferably polyethylene glycols, and the number average molecular weight thereof is not particularly limited, but preferably 300 to 100,000, more preferably 60.
It is 0 to 10,000, particularly preferably 1,000 to 5,000. The content of the modified polyester of polyalkylene glycol is preferably from 3 to 10% by weight, and the preferred content is from 4 to 8% by weight.

Examples of the aliphatic dicarboxylic acid as the modifying component of the modified polyester include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like, and adipic acid, suberic acid, azelaic acid are preferable, and adipic acid is particularly preferable. Acids are preferably used. It is preferably 3 to 10% by weight, and preferably 4 to 8% by weight, based on the total weight of the polyester of the aliphatic dicarboxylic acid, but when the polyalkylene glycol and this aliphatic dicarboxylic acid are used together, the total amount is 3 ~ 10 wt% is preferred, especially 4 ~
8% by weight is preferred.

The modified polyester polyether dicarboxylic acid is preferably polyethyleneoxydicarboxylic acid, polypropyleneoxydicarboxylic acid, poly (ethylene / propylene) oxydicarboxylic acid, polytetramethyleneoxydicarboxylic acid or a copolymer thereof, and the like. From the viewpoint of the polymerization reactivity and the plane stability of the film, it is more preferable to use the polyethyleneoxydicarboxylic acid ester represented by the following formula.

R ⁵ OOCCH ₂ — (OCH ₂ CH ₂ ) _q —OCH ₂ COOR ⁶ Here, R ⁵ and R ⁶ are hydrogen or an alkyl group having 1 to 8 carbon atoms, and q is a positive integer. The modification ratio of the polyether dicarboxylic acid component is 2% of the total polyester weight.
-30% by weight, preferably 5-15% by weight, particularly preferably 7-12% by weight.

The modified polyester resin useful in the present invention has an intrinsic viscosity of preferably 0.45 to 0.85, particularly preferably 0.50 to 0.70.

The modification ratio of the modified polyester resin may be such that it can be copolymerized with other components or blended with other resins as long as the plastic film can be used. The resin to be blended is preferably a polyester resin.

The constitution of the laminated plastic film useful in the present invention has at least one layer of the above modified polyester film. However, in the case of three or more layers, even if the modified polyester layer is the inner layer of the laminated constitution, It may be in the outer layer, but it is preferable that it is in the inner layer because it is difficult for the plastic film, particularly a photographic film, to have a curl.

Examples of the component of the resin layer used together with the modified polyester film of the laminated plastic film useful in the present invention include polyethylene terephthalate, polyethylene naphthalate, polysulfone, polyamide, polyaramid, polyimide and the like. Among them, polyethylene terephthalate, polyethylene naphthalate Phthalate is preferred. For polyethylene naphthalate, polyethylene-2,6-
Naphthalate, polyethylene-1,5-naphthalate and polyethylene-2,7-naphthalate are preferred. Among them, especially polyethylene terephthalate and polyethylene-2,6-
A naphthalate polyester resin is preferred. When the laminated structure has three or more layers, the resin layer may be in the inner layer or the outer layer portion, but the outer layer portion is preferable. The two outermost layers may be made of the same resin or different resins.

The polyethylene terephthalate resin and the polyethylene-2,6-naphthalate resin which are particularly preferably used in the outermost layer of the laminated plastic film useful in the present invention are not particularly limited in quality, but when used in a photographic film, they are particularly photographic. A grade is preferable. Further, the intrinsic viscosity of the polyester resin is preferably 0.50 to 0.85,
Particularly, 0.55 to 0.70 is preferable.

The most preferable laminated film having a three-layer laminated structure comprises a polyethylene terephthalate resin layer and / or a polyethylene naphthalate resin layer as two outermost layers and a modified polyester resin layer containing a metal sulfonate group as an inner layer. It is a thing.

The laminated film useful in the present invention is characterized in that, when the thickness thereof is divided into two equal parts, the layer structure on both sides of the divided part is asymmetric. The fact that the laminated structure on both sides of the laminated film is asymmetric with respect to the position where the laminated film is divided into two equal parts in the thickness direction means that the constituent components of the resin, the properties of the resin, the layer constitution, film forming conditions, etc. Are changed, and are appropriately selected and combined. Asymmetrical here means that they are physically, mechanically, or chemically different, and are composed of layers of different materials (layers of completely different nature), the order in which the layers are formed, the thickness, and the constituents (copolymerization composition). The types of units), the amounts of constituent components (amount ratio of constituent units of copolymerization), and the physical properties such as intrinsic viscosity are different.

The method for measuring the asymmetry of these laminated films can be carried out by using various analytical instruments and is not particularly limited, but regarding the layer constitution, a cross section of the film is observed under a microscope and a micrograph is taken. Can be done. Further, while observing the film under a microscope, each layer is scraped off, or the film is divided into halves, each of which is scraped from above and below to obtain an analyte of each of the upper and lower layers, and hydrolysis is performed for liquid chromatography and NMR.
It may be measured by various measuring devices such as, etc., or the analyte may be dissolved in a solvent and then NMR, GPC (gel permeation chromatography), intrinsic viscosity, etc. may be measured, or the analyte may be directly powdered. Can be mixed with X-ray spectroscope or KBr to measure IR (infrared spectrophotometer), etc., and as a result, it is asymmetrical in terms of absolute quantity or peak position and intensity difference of the measurement result corresponding to it. The sex can be measured.

The modified polyester resin can be synthesized by a conventionally known polyester production method. For example, in the esterification reaction, both direct esterification of an acid component with a glycol component and esterification by a transesterification method with glycol using an acid component as a dimethyl ester can be used. Further, it is particularly preferable to use the acid component as the modifying component in advance in the form of ethylene glycol diester (specifically, ethylene glycol dihalf ester). At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for the esterification and a polymerization reaction catalyst such as antimony trioxide in the polymerization reaction. Regarding the polyester constituents and the synthetic method described above, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pages 103 to 136, or "Synthetic Polymer V" (Asakura Shoten) , 1971) The description on pages 187-286 can be referred to.

Specific methods for synthesizing the modified polyester resin are described in US Pat. No. 4,217,441 and JP-A-5-210199, and the modified polyester resin useful in the present invention can be synthesized by these methods.

Examples of the catalyst used for this transesterification include acetates, fatty acid salts and 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 metal salt of a hydroxide or an aliphatic carboxylic acid, a quaternary ammonium salt or the like within a range that does not hinder the reaction or color the resin during the transesterification and / or the polymerization, and among others, Sodium hydroxide, sodium acetate, tetraethylammonium hydrate and the like are preferable, and sodium acetate and tetraethylammonium hydrate are particularly preferable.

In order to obtain the modified polyester, the acid component and the glycol component may be transesterified, and then the above-mentioned modifying component may be added to carry out the melt polymerization, or the modified component may be added before the transesterification. However, melt polymerization may be carried out after transesterification, or a known synthesis method such as solid-phase polymerization of the resin obtained by melt polymerization may be employed.

Examples of the catalyst used for polyester polymerization (after transesterification) include antimony trioxide, zinc oxide, manganese dioxide, titanium dioxide and the like.
Of these, antimony trioxide is preferable.

Both of the polyesters are phosphoric acid,
Phosphorous acid and esters thereof and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate,
(Titanium dioxide, etc.) may be contained, or inorganic particles may be blended with the polymer after polymerization. Further polymerization step, a pigment at any stage after polymerization,
An ultraviolet absorber, an antioxidant, a matting agent, a slip agent, a stabilizer, a surfactant, a dispersant, an anti-adhesive agent, a softening agent, a fluidity imparting agent and the like may be added.

The above-mentioned antioxidant is not limited to its kind, and specific examples thereof include hindered phenol compounds, allylamino compounds, phosphite compounds, thioester compounds and the like. Can be used. Among these, hindered type is preferable. In producing the modified polyester, it is most preferable to add the antioxidant before extrusion. In order to obtain excellent photographic performance without increasing the turbidity of the laminated film, the content is usually 0.01 to 2% by weight, preferably 0.1 to 0.5% by weight, based on the modified polyester. %. The antioxidants may be used alone or in combination of two or more.

The polyester may contain various additives. For example, a dye may be added to the polyester for the purpose of preventing a light piping phenomenon (fogging) which occurs when light enters from the cross section of a support film coated with a photographic emulsion layer. The type of this dye is not particularly limited, but in the film forming process,
Those having excellent heat resistance are preferable, and examples thereof include anthraquinone chemical dyes.

The laminated film useful in the present invention has a structure in which two or more kinds of resin layers are laminated in three or more layers, and such a resin layer is combined to form a laminated film of three layers. Explaining with an example, it can be manufactured as follows. That is, for example, three kinds of resins are dried by three separate vacuum dryers, the respective resins are put into three separate extruders, and melt-extruded, and then the respective melted resins are vertically placed in one conduit. In this way, three layers of molten resin form a laminar flow in the conduit and are extruded from the extrusion die having one slit onto the cooling drum to form one unstretched sheet. Alternatively, as another method, Introducing three types of molten polymer into one die, from an extrusion die with three slits, or from an extrusion die that allows three slits to be combined into one slit in the die, The three laminar flow layers were extruded on a cooling drum to form one sheet, and then cooled and solidified on the cooling drum to obtain an unstretched film, which was then stretched in the longitudinal direction by a longitudinal stretching machine. , Then horizontally Stretched in Shin machine is further followed by heat-setting at the same cabin heat setting zone method of laminating a molten state to obtain a biaxially stretched film, it is a useful method in the present invention. Another method is another position film forming method in which three kinds of molten polymers are separately extruded onto a cooling drum and cooled and solidified, which is also useful in the present invention. These are also called coextrusion methods.

Besides this, there is a method of laminating and laminating separately formed films. That is, three kinds of resins are separately formed into unstretched films or uniaxially stretched films, which are coated with an anchor agent, an adhesive, etc., and these three kinds of films are laminated and laminated, and then the two films are laminated. It is a method of axially stretching and heat setting.
However, this method is not practical in terms of quality because the process is complicated and the equipment cost is too high, and the coextrusion method is preferable because of its simplicity.

The temperature at which the modified polyester resin is melted in the extruder is in the range of 260 to 320 ° C. Preferably 280
~ 310 ° C. In the case of coextrusion, the modified polyester resin is preferably melted at the same temperature as the resin used for the outermost surface layer, for example, polyethylene terephthalate resin.

The stretching conditions of the laminated film are not particularly limited, but generally, the glass transition temperature (Tg) of a plurality of resin layers
The high temperature resin is biaxially stretched in the temperature range of Tg to Tg + 100 ° C. At this time, the following methods A, B and C can be adopted in the same manner as the stretching method of the polyethylene terephthalate layer. The stretching ratio is preferably in the range of 4 to 16 times in area ratio. The heat setting can be performed in the temperature range of 150 to 240 ° C.

(A) A method in which an unstretched sheet is first stretched in the longitudinal direction and then in the transverse direction (B) A method in which an unstretched sheet is first stretched in the transverse direction and then in the longitudinal direction (C) Unstretched A method in which a sheet is stretched in the longitudinal direction in one or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction.

The layers such as the resin layer, the outermost layer, and the inner layer are films having a certain thickness of the resin serving as a support, such as an undercoat layer, an antistatic layer and an emulsion layer. Is distinct from the layers of.

The total thickness of the laminated structure film according to the present invention is not particularly limited and can be arbitrarily determined according to the application, but is usually 40 to 250 μm, particularly preferably 65 to 180 μm.

The syndiotactic polystyrene film is a film of a polymer having a main chain of polystyrene main chain having a racemo chain or a composition containing the polymer. The syndiotactic polystyrene polymer or composition is The legal method is JP 62-117708 A, JP 1
-46912 and 1-178505. This main chain chain has ¹³ C-
It can be quantified by measuring the carbon atom at the 1-position of the benzene ring using NMR. Racemo chain is 85% with 2 chains
As described above, it is preferably 75% or more in 3 chains and 50% or more in 5 chains. The syndiotactic polystyrene film can be formed in the same manner as the method for forming the polyethylene terephthalate film, although the conditions such as the melting temperature and the stretching temperature are slightly different. For example, JP-A-3-1318
The syndiotactic film can be formed by the method described in the specification of No. 43.

The thickness of the plastic film according to the present invention is preferably 100 μm or less for the purpose of miniaturization of a camera. For this reason, the plastic film as a photographic support has a large mechanical strength and is hard to be curled. ,
It must be dimensionally stable. Specific examples of the plastic film having such properties include polyethylene terephthalate film, polyethylene-2,6-naphthalate film, laminated polyester film of polyester and modified polyester of the former two, and syndiotactic polystyrene. Can be used particularly usefully in the present invention.

The plastic film having an antistatic layer of the present invention comprises a photographic support, a drawing film and an O film.
It can be widely used as a HP film, marking film, animation film, etc.

<Undercoat layer> When the plastic film used in the present invention is used as a support, a functional layer such as an antistatic layer and a photosensitive emulsion layer of a photographic film are provided on the support. The undercoating treatment is carried out in advance for the purpose of enhancing their coatability and maintaining their strong adhesiveness to the support.

In the case of a cellulose triacetate or polycarbonate film, a method of applying an undercoating coating solution in which a hydrophilic polymer is dissolved or dispersed in a solvent which is soluble or swellable in these supports is employed. Examples of the soluble or swelling solvent include acetone, methylene chloride, ethylene chloride, methanol, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoacetate and dimethylformamide. However, it is not limited thereto.

Since the undercoating method of polyethylene terephthalate can be applied to the undercoating of the above polyester film useful in the present invention, polyethylene terephthalate will be described below as an example. The subbing of polyethylene terephthalate can be carried out in any of the processes before stretching during film formation, after uniaxial stretching, after biaxial stretching and before heat setting, or after biaxial stretching and heat setting. Polyethylene terephthalate undergoes oriented crystallization after being biaxially stretched and heat-fixed, and it becomes relatively difficult for an upper object such as an emulsion layer to adhere. Therefore, it is common to apply an undercoating agent before the completion of oriented crystals. In order to apply the undercoating agent before heat setting, the following known undercoating agents and undercoating methods can be used. For example, U.S. Patent Nos. 2,852,378 and 3
58,608, 3,630,741, 2,627,088, 2,698,235, JP-A-51-135991,
Japanese Patent Publication No. 52-48312, Belgian Patent Nos. 721,469 and 742,7
No. 69 etc. or vinyl halogenoester containing copolymer and vinyl chloride and / or vinylidene chloride containing copolymer, described in JP-B-58-58661, JP-B-58-55497, JP-A-52-108114 and the like. Copolymers containing diolefins as monomers,
Acrylic polymers described in JP-A-61-204242, JP-A-61-204241 and the like, JP-B-57-971, JP-A-61-204240, JP-A-6-204240
0-248231, polyester-based polymers described in JP-A-3-265624 and the like can be mentioned.

The undercoating after the biaxial stretching heat setting is carried out by an organic solvent-based undercoating, or a so-called etching solvent (eg phenol, cresol, resorcin, or oxidizer) which etches polyethylene terephthalate to bond the undercoating material by the anchoring effect. There is also a method of applying an organic solvent-based or water-based undercoat liquid containing water chloral, chlorophenol, etc.).
This is because polyethylene terephthalate has a regular structure in which adhesion is difficult, and the surface structure is loose or chemically changed. For this purpose, surface activation treatment such as mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone treatment and the like is preferable. Good adhesive strength can be obtained by directly coating the photographic emulsion after the above treatment, but in order to further strengthen the adhesive strength, a further subbing layer may be provided, and a photographic emulsion layer may be formed on the undercoating layer. A good film is obtained. Even with a water-based undercoating agent, the adhesiveness can be easily improved by utilizing the above various treatments as a pretreatment. For example,
N-Butyl methacrylate of the method described in JP-A-55-67745, JP-A-59-19941 and the like: quaternary copolymer latex composed of t-butyl methacrylate, styrene and 2-hydroxyethyl methacrylate, surfactant , An aqueous subbing liquid consisting of a curing agent is applied and dried, followed by corona discharge treatment again, and then a gelatin aqueous solution such as an antihalation layer or an emulsion layer is applied to the photographic emulsion layer side to improve the adhesive property. It is possible to obtain a light-sensitive material having good quality. On the other side of the antistatic layer, the same treatment as above or an undercoat layer is applied, and then an antistatic coating solution is directly applied and an antistatic layer binder such as cellulose diacetate is applied in advance and then the antistatic coating is applied. A desired photographic light-sensitive material can be finished by applying the liquid as an organic solvent-based liquid.

<Antistatic Layer> The antistatic layer of the π-electron conductive polymer of the present invention may or may not have an undercoat layer on the plastic film, but the π of the present invention may be directly or indirectly. It is obtained by applying an antistatic coating liquid containing an electronically conductive polymer. The antistatic layer may be the uppermost layer or an upper layer such as a protective layer may be provided on the antistatic layer. Also, on the photographic photosensitive layer,
It may be between or below. The undercoating liquid and the antistatic coating liquid can be applied by a method such as dip coating, air knife coating, spraying or extrusion coating using a hopper described in US Pat. No. 2,681,294. Also U.S. Patent 3,508,847,
No. 2,941,898, No. 3,526,528, etc., two or more layers may be coated at the same time, or a photographic light-sensitive material may be dipped in the composition of the present invention.

The coating amount of the π-electron conductive polymer of the antistatic coating liquid of the present invention is in order to obtain good antistatic performance.
It is preferably 0.0001 to 2 g / m ² , particularly 0.001 to 1
It is preferably g / m ² .

<Back Layer> A layer provided on the opposite side of a photosensitive material having a photosensitive layer on one side of a support without the photosensitive layer is called a back layer. A back layer is provided depending on the type of silver halide light-sensitive material. A hydrophilic polymer binder is often used for the back layer, but gelatin similar to the binder for the photosensitive layer is most preferably used. Alkali-treated ossein gelatin, acid-treated ossein gelatin, acid-treated pigskin gelatin, phthalated Various gelatins such as gelatin derivatives such as gelatin are used. If necessary, other hydrophilic polymers, matting agents, slip agents, surfactants, hardeners, dyes, thickeners, polymer latices, the above antistatic agents and the like can be added to the gelatin back layer.

<Photosensitive Layers such as Silver Halide Emulsion Layer> The silver halide photosensitive materials according to the present invention include ordinary black-and-white photographic light-sensitive materials (for example, photographing black-and-white photographic light-sensitive materials, printing photographic light-sensitive materials, X-ray photographs). Photosensitive materials, etc.), ordinary color photographic photosensitive materials (eg, color negative film, color reversal film, color positive film, etc.)
Various light-sensitive materials (hereinafter sometimes abbreviated as color film) can be mentioned.

The binder of these photosensitive layers is mainly made of gelatin, and the photosensitive layer contains silver halide grains, a polymer latex, an oil agent for dispersing a coupler and the like as described below.

The silver halide photosensitive layer and the like will be briefly described below.

Silver halide grains and other additives of the silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention, for example, chemical sensitizers, spectral sensitizing dyes, hardeners, surfactants, and colors. There are no particular restrictions on couplers, and for example, Research Disclosure (Resear
ch Disclosure) No. 308119 (hereinafter abbreviated as RD308119) can be used. The description location is shown below.

[Item] [Page of RD308119] Iodine composition 993 IA Item Manufacturing method 〃 〃 and 994 E Item Crystal habit Normal crystal 〃 Twin 〃 〃 Epitaxial 〃 〃 Halogen composition Uniform 993 IB Item uniform Not 〃 Halogen conversion 993 I-C item Halogen substitution 〃 Metal-containing 993 I-D item Monodisperse 995 I-F item Solvent addition 〃 Latent image forming surface 995 I-G inner surface 〃 Applied photosensitive material Negative 995 Item I-H Positive (including internal fog grains) 〃 〃 Mixed emulsion 995 Item I-J Desalting 995 Item II-A The silver halide emulsion was subjected to physical ripening, chemical ripening and spectral sensitization. Use one. Additives used in such processes, Research Disclosure No. 17643,
Same No. l8716 and same No. 308119 (hereinafter referred to as RDl7643,
(Abbreviated as RDl 8716 and RD308119). The description location is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 Item III-A 23 648 Spectral sensitizer 996 IV-A, B, C, D, 23 to 24 648 to 9 E ~ J Item Supersensitizer 996 IV-A ~ E, J item 23 ~ 24 648 ~ 9 Antifoggant 998 VI 24 ~ 25 649 Stabilizer 998 VI 24 ~ 25 649 The photographic additives that can be used are also in the above RD. Have been described.
Descriptions are shown below [Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII-C 25-26 XIII-C Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer 1011 XX-B (included in the photosensitive material) Also use various couplers And specific examples thereof are also described in the above RD. The relevant description is shown below.

[Items] [Page of RD308119] [RD17643] Yellow coupler 1001 Item VII-D 25 VII-C to G Magenta coupler 1001 VII-D 25 VII-C to G Cyan coupler 1001 VII-D 25 VII-C to G Colored coupler 1002 VII-G 25 VII-G DIR coupler 1001 VII-F 25 VII-F BAR coupler 1002 VII-F Other 1001 VII-F useful residue releasing coupler Alkali Soluble 1001 VII-E coupler The additive used can be added by the dispersion method described in RD308119XIV.

For the color light-sensitive material, the above-mentioned RD308119 VII-
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided. Also, the aforementioned RD308119 VII-K
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section can be adopted.

To process the photographic film of the present invention, for example, T.I. H. James, The Theory of The Photographic Process 4th Edition
ThePhotographic Process Forth Edition) Page 291 ~
Page 334, and the Journal of the American Chemic
Al Society), Vol. 73, page 3,100 (1951), known developers can be used. Color photographic light-sensitive materials are described in RD17643, pages 28-29, RDl8716.
The development can be carried out by a usual method described on page 615 and XIX of RD308119.

<Magnetic Recording Layer> If necessary, a silver halide photographic light-sensitive material may be coated with a magnetic recording material on the upper surface of the photosensitive layer or on the upper surface of the back layer for the following purposes.

For example, a stripe-shaped magnetic recording layer in which ferromagnetic fine particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and photographing conditions. KAISHO 50-62627 publication, JP 49-4503 publication,
U.S. Pat. Nos. 3,243,376 and 3,220,843 are described, and the necessary transparency is obtained by selecting the amount and size of magnetic particles on the back surface of the silver halide photographic light-sensitive material. Providing a transparent magnetic recording layer, U.S. Patent Nos. 3,782,947, 4,279,945 and 4,302,
No. 523, etc. In addition, US patent
No. 4,947,196 and WO 90/04254 describe a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic substance capable of magnetic recording on the back surface of a photographic film.

As described above, in the silver halide photographic light-sensitive material, for example, various kinds of information about the silver halide photographic light-sensitive material such as the type / manufacturing number of the photographic light-sensitive material, manufacturer's name, emulsion No. Time, aperture, exposure time,
Lighting conditions, filters used, weather, size of shooting frame,
Various information when shooting with the camera, such as camera model, anamorphic lens usage, etc., such as the number of prints, filter selection, customer color preference, trimming frame size, and other information necessary for printing , Various information obtained at the time of printing such as the number of prints, selection of filters, customer's color preference, trimming frame size, etc.
It is convenient to enter the customer information and the like in order to record the above-mentioned matters not only for management but also for improving print quality and efficiency of printing work.

In a conventional silver halide photographic light-sensitive material, it is impossible to input all the above information, and it is possible to slightly obtain information such as a shooting date / time, aperture, and exposure time at the time of shooting. I was just typing in. Moreover, at the time of printing, it was completely impossible to input the above information into the photographic light-sensitive material because there was no means for that.

Since the magnetic recording method is easy to record / reproduce, the use of the magnetic recording method for inputting the above various information to the silver halide photographic light-sensitive material has been studied, and various techniques are as described above. Proposed.

By providing these magnetic recording layers, it becomes possible to record the above-mentioned various information in the silver halide photographic light-sensitive material, which has been difficult in the past, and also to record voice and image signals in the future. Have sex.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-adhered iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder, etc. are used. it can.

When the transparent magnetic recording layer is provided on the photosensitive layer side, a hydrophilic binder such as gelatin is used as the binder of the magnetic recording material. In the case of a hydrophilic binder, gelatin is preferably used. When the magnetic recording layer is provided on the back side without the photosensitive layer, a hydrophobic solvent-soluble binder such as cellulose nitrate is used.

[0155]

EXAMPLES The present invention will be described in detail below with reference to Examples, but it goes without saying that the present invention is not limited thereto.

Example 1 A backing layer and a halogenated layer were formed on a support in which an antistatic layer and a subbing layer containing the π-electron conductive polymer shown in Table 1 of the present invention were coated on the following plastic film. Applying emulsion layers for silver printing respectively,
It was submitted to the test.

<Plastic film> A biaxially stretched and heat-set polyethylene terephthalate film having a thickness of 100 μm (hereinafter sometimes abbreviated as PET), also having a thickness of 80 μm
Polyethylene-2,6-naphthalate film (hereinafter PE
N), and a three-layer laminated film (PET / M / PET) of 90 μm thick modified polyester (hereinafter M) and polyethylene terephthalate with a thickness of 90 μm.
(Indication) was prepared as follows.

Commercially available polyethylene terephthalate film and polyethylene-2,6-naphthalate film were used, and a modified polyester laminated film was prepared as follows.

<< Synthesis of Modified Polyester >> Terephthalic Acid
To 100 parts by weight and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate monohydrate was added, and an esterification reaction was carried out by a conventional method. The obtained product was 28 parts by weight of ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) (5 mol% / total acidic content), polyethylene glycol (number average molecular weight 300
0) 8.1 parts by weight (7% by weight / polymer), antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight were added. Then gradually raise the temperature and reduce the pressure, 280 ℃, 0.5mmHg
Polymerization was carried out to obtain a modified polyester resin having an intrinsic viscosity of 0.57.

<< Preparation of Three-Layer Laminated Film >> The above modified polyester resin (M) and a commercially available polyethylene terephthalate resin (PET) having an intrinsic viscosity of 0.65 are separately vacuum dried at 150 ° C., and then three extruders are used. (2 units are polyethylene terephthalate resin, 1 unit is modified polyester resin) Melt extruded at 285 ° C, 3 layers are made of modified polyester as the core of the middle layer, and polyethylene terephthalate is provided on the outer layers on both sides of the sandwich type structure. And the ratio of the thickness of each layer (PET / M / PET) is 3/10/7
And the amount is adjusted so that the total film thickness of the finished product is 100 μm, and the layers are joined in a T-die and extruded.
A laminated unstretched sheet was obtained by rapid cooling and solidification while closely contacting with a cooling drum by an electrostatic contact method. Then at 85 ° C vertically
It was stretched 3.5 times. Then after stretching 3.5 times in the transverse direction at 95 ° C,
A biaxially stretched laminated film was obtained by heat setting at 210 ° C.

<Formation of undercoat layer> Both surfaces of each film were subjected to a corona discharge treatment of 8 W / m ² · min, and one surface was coated with the following antistatic undercoat coating solution a-1 to a dry film thickness of 0.8 μm. As a result of undercoating, a subbing layer A-1 was prepared. Further, the undercoat coating solution b-1 shown below was undercoat-coated on the opposite surface to a dry film thickness of 0.8 μm to obtain an undercoat layer B-1.

[0162] << Antistatic Subbing Coating Solution a-1 >>       Butyl acrylate 30% by weight       20% by weight t-butyl acrylate       Styrene 25% by weight       2-hydroxyethyl acrylate 25% by weight     Copolymer latex liquid (solid content 30%) 270 g     Compound (C-6) 0.6 g     Hexamethylene-1,6-bisethyleneurea 0.8 g     ASP- (I) -6- (a) 300 g     Make up to 1 liter with water.

[0163] <Subbing coating solution b-1>       Butyl acrylate 40% by weight       Styrene 20% by weight       Glycidyl acrylate 40% by weight     Copolymer latex liquid (solid content 30%) 270 g     Compound (C-6) 0.6 g     Hexamethylene-1,6-bisethyleneurea 0.8 g     Make up to 1 liter with water.

ASP (I) -6- of the π-electron conductive polymer of the present invention in the antistatic undercoat liquid a-1 of the above sample.
As shown in Table 1 in place of (a), various antistatic undercoat layers of A-1 using a dispersion of a π-electron conductive polymer were obtained.

Subsequently, the undercoat layer B-1 and the undercoat layer A-1
Corona discharge of 8 W / m ² · min is applied on the above, and the following coating liquids b-2 and a-2 are respectively dried on each layer.
It was applied so as to have a thickness of 1.0 μm and 0.1 μm to form an undercoating upper layer B-2 layer and a undercoating upper layer A-2 layer, respectively, to obtain an undercoated plastic film.

[0166] << Undercoating upper layer coating liquid b-2 >>     Gelatin 20 g     Compound (C-6) 0.2 g     Compound (C-7) 0.2 g     N, N ', N "-Trisacryloyl-1,3,5-trimethylenetriamine 0.1 g     0.1 g of silica particles with an average particle size of 3 μm   Made up to 1 liter with water.

[0167] << Undercoat layer coating liquid a-2 >>     Compound (C-6) 0.2 g     Compound (C-7) 0.2 g     N, N ′, N ″ -Trisacryloyl-1,3,5-trimethylenetriamine 0.1 g     Gelatin 10 g     0.1 g of silica particles with an average particle size of 3 μm     Make up to 1 liter with water.

[0168]

[Chemical 16]

Using these three types of undercoat and antistatic plastic films as a support, the above-mentioned undercoat upper layer A-2 is prepared.
And both sides of B-2 were subjected to corona discharge of 25 W / m ² · min,
The following back layer coating solution b-3 and back layer protective layer coating solution b-4 were coated on B-2, and the amount of gelatin was 2.0 g.
/ M ² and 1.5 g / m ² so as to form a back layer B-4. On the other hand, the undercoat layer A-2 was coated with the following emulsion layer coating solution formulation to prepare an emulsion layer (coating gelatin amount 2.0 g /
m ² ), and an emulsion protective layer (coated gelatin amount 1.
0 g / m ² ) was coated in two layers at the same time, respectively, and dried to prepare a photographic light-sensitive material for silver halide printing, which was then subjected to a test.

<Formation of Back Layer and Photosensitive Layer><< Preparation of Back Layer Coating Solution b-3 >> 36 g of gelatin was swelled in water and dissolved by heating, and then the compound (C-1) was used as a dye.
1.6 g, compound (C-2) 310 mg, compound (C-3) 1.9
g, and 2.9 g of compound (N) as an aqueous solution,
Next, 11 ml of 20% saponin aqueous solution, 5 g of compound (L _x -1) were added, and 63 mg of compound (C-4) was added as a methanol solution. To this solution, 800 g of sodium polystyrene sulfonate water-soluble polymer was added as a thickener to adjust the viscosity, pH was adjusted to 5.4 with an aqueous citric acid solution, and 1.5 g of a reaction product of polyglycerol and epichlorohydrin was added. Glyoxal 144mg added, water added 960
The coating liquid b-3 for the back layer was prepared by finishing to ml.

[0171]

[Chemical 17]

[0172]

[Chemical 18]

<< Preparation of Back Layer Protective Layer Coating Solution b-4 >> 50 g of gelatin was swollen in water and dissolved by heating, and then 340 mg of 2-sulfonate-bis (2-ethylhexyl) succinate ester sodium salt, Sodium chloride (3.4 g), glyoxal (1.1 g), and formalin (540 mg) were added. Furthermore, spherical polymethylmethacrylate having an average particle diameter of 4 μm was added as a matting agent so as to have a concentration of 40 mg / m ² ,
Coating liquid for protective film layer b-
4 was prepared.

<< Preparation of Silver Halide Emulsion Layer Coating Solution for Printing >><< Preparation of Silver Halide Emulsion Coating Solution >> After adding 9 mg of the compound (A) to the emulsion shown below, 0.5N sodium hydroxide solution was used to adjust to pH6. .5 and then compound (T) 36
Add 0 mg, and saponin 20% per mol of silver halide
5 ml of aqueous solution, 180 mg of sodium dodecylbenzene sulfonate, 80 mg of 5-methylbenztriazole, 43 ml of compound (L _x -2) were added, 60 mg of compound (M), and sodium polystyrene sulfonate water-soluble polymer as a thickener. 280 mg was sequentially added, and the solution was adjusted to 475 ml with water to prepare a silver halide emulsion coating solution.

<< Preparation of Emulsion >> A silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows. Silver nitrate 60
An aqueous solution containing 23.9 mg of potassium pentabromorhodium salt, sodium chloride and potassium bromide and an aqueous solution of silver nitrate per g in an aqueous gelatin solution are simultaneously mixed with stirring at 40 ° C. for 25 minutes to give an average particle size of 0.20 μm. A silver chlorobromide emulsion was prepared.

After adding 200 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer to this emulsion,
It was washed with water and desalted.

To this was added 20 mg of 6-methyl-4-hydroxy-1,3,
After adding 3a, 7-tetrazaindene, sulfur sensitization was performed. After sensitizing with sulfur, add gelatin and use it as a stabilizer.
An emulsion was prepared by adding 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene and then making up to 260 ml with water.

<< Preparation of Coating Solution for Emulsion Protective Film >> Gelatin 50
Water was added to mg and dissolved at 40 ° C after swelling, then 500 ml of a 1% aqueous solution of compound (Z) as a coating aid, compound (N) as a filter dye, and 50 mg of compound (D) were sequentially added, followed by quenching. The pH was adjusted to 6.0 with the acid solution. Matting agent (particle size
4.0 μm amorphous silica) is added to 40 mg / m ² ,
A coating solution for emulsion protective film was prepared.

[0179]

[Chemical 19]

[0180]

[Chemical 20]

<Development Processing><< Processing Conditions >> Process Temperature (° C.) Time (sec) Development 34 15 Fixing 34 15 Washing with water Normal temperature 10 Drying 40 9 <Developer formulation> (Development composition A) Water 150 ml Ethylenediaminetetraacetic acid diester Sodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide The pH of the solution is 10.9. Amount of potassium bromide 4.5 g (Development composition B) Water 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% W / W aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg Development When the solution was used, the developing composition A and the developing composition B were dissolved in this order in 500 ml of water, and water was added to make 1 liter.

<< Fixing Solution Formulation >> (Fixing Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5
g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / W aqueous solution) 8.1 ml (Fixing composition B) Water 17 ml Sulfuric acid (50% W / W aqueous solution) 5.8 g aluminum sulfate (aqueous solution containing 8.1% W 2 W in terms of Al ₂ O ₃ ) 26.5 g When fixing solution was used, the above fixing composition A and fixing composition B were dissolved in this order in 500 ml of water, and water was added to prepare 1 It was used after finishing to liter. The pH of this fixer was about 4.3. The W / W represents weight / weight, and W / V represents weight / volume.

<Evaluation Method><< Ash Adhesion Test >> Two exposed and developed samples were each cut into 10 cm square pieces, and the humidity was adjusted in an atmosphere of 23 ° C. and 40% RH, and the samples were subjected to the following tests. Place the sample on the rubber plate with the emulsion side facing up under the same conditions as above, charge the emulsion roller side 10 times with a rubber roller, and after 1 minute, put the cigarette ash prepared separately on the paper. In the densely and uniformly widened upper space, hold the sample (with the emulsion side down) with clips of an insulating material and position the sample surface parallel to the ash plane with a vertical insulating worm gear. Using a simple device that descends in parallel, the antistatic effect was observed by approaching the ash and evaluating the degree to which the ash adhered to the sample. The sample was lowered at a speed of 1 cm per minute so that it was parallel to the ash surface, and the height at which ash adhered was observed. In this test, the tester wears rubber gloves to remove the static electricity from the hand holding the sample.

Evaluation level A: No adhesion at all when the sample is contacted with ash B: When the sample is contacted with ash, ash adheres to the sample, but when the distance between the sample and ash is 1 cm, ash does not exist at all. Level C that does not adhere: Ash adheres when the distance between the sample and ash is 1 cm, but 2
Level D that does not adhere at a distance of cm: Ash adheres when the distance between the sample and ash is 2 cm, but 4
Level E which does not adhere at a distance of cm: Ash adheres when the distance between the sample and ash is 4 cm, but 6
Level F that does not adhere at a distance of cm: Ash adheres even if the distance between the sample and ash is 6 cm, but 8
Level G that does not adhere at a distance of cm: Ash adheres even if the distance between the sample and ash is 8 cm, but 10
Level H that does not adhere at a distance of cm: Level where ash adheres even if the distance between the sample and ash is 10 cm or more << Static mark test >> Unexposed sample at 25 ° C, 25% R
After the humidity was controlled for 2 hours in the atmosphere of H, the emulsion surface side of the sample was rubbed with a neoprene rubber roller in a dark room under the same humidity control condition, and then development processing was performed to examine the degree of generation of static marks. The evaluation is as follows. A: No static marks were recognized at all B: Very few static marks were recognized C: Some static marks were recognized D: Static marks were significantly recognized E: Static marks were almost completely covered F: observed on the sample: Scratch test in which the entire surface of the sample was blackened. Subbing The plastic film processed to the upper layer B-2 was conditioned for 3 hours in an atmosphere of 23 ° C. and 80% RH,
On the film 1.0 kg of 10 cm x 10 cm hard sponge
A weight was put on the slide, and the number of scratches was counted. The results are shown in Table 1.

[0185]

[Table 1]

<Evaluation and Results> As shown in Table 1, it was found that when the coefficient of variation is 50% or more, the antistatic performance is lowered, and when the average particle size is increased, the antistatic performance is further deteriorated. It was also found that the easiness of scratches depends on the coefficient of variation and the particle size. Within the range of the average particle diameter and the coefficient of variation of the present invention, the power failure prevention performance and the scratch resistance are also good. Although not shown in Table 1, a plastic film (support)
There was no difference between them.

Example 2 In the process of forming a polyethylene terephthalate film, both sides were subjected to in-line subbing and antistatic treatment, and medical X-ray emulsion layers were coated on both sides of the film to prepare a silver halide X-ray photograph. A photosensitive material for use was prepared and subjected to a test.

<Formation of Polyethylene Terephthalate Film and Formation of Undercoat Layer and Antistatic Layer> Commercially available photographic grade polyethylene terephthalate resin chips having an intrinsic viscosity of 0.65 were vacuum dried at 150 ° C. for 8 hours, and then moisture was blocked. Keep the chip at 150 ° C with the blue dye (Bayel dye Macr
olexBlue RR) with a rotary mixer, melt-mix and color with an extruder, melt-extrude in layers from a T-die at 290 ° C, and apply a static charge onto a rotating 50 ° C cooling drum to bring the resin sheet into close contact and quench. Solidified to form an unstretched sheet, and subsequently, in a roll-type longitudinal stretching step, a uniaxially stretched film obtained by stretching the unstretched sheet 3.5 times in the longitudinal direction at 85 ° C., followed by the in-line subbing liquid a -10 and b-10 were applied on both sides to form undercoat layers A-10 and B-10 (applied so that the film thickness after stretching would be 0.1 μm). Further, subsequently, in a tenter-type transverse stretching step, the film was stretched 3.5 times in the transverse direction at 95 ° C. and then heat-set at 210 ° C. to obtain an undercoated blue colored biaxially stretched film having a thickness of 180 μm. Next, undercoat layer A-
10 and B-10 both sides were subjected to corona discharge treatment of 8 W / m ² · min, and undercoat liquids a-11 and b-11 were dried on both sides to a dry film thickness of 0.8.
Undercoat layers A-11 and B-11 were coated so as to have a thickness of μm.

<< Undercoating Liquid and Antistatic Coating Composition >><< Inline Undercoating Liquid a-10 and b-10 Formulation >> An aqueous copolyester was synthesized for the following inline undercoating liquid.

<< Synthesis of Aqueous Copolyester >> 37 parts by weight of dimethyl terephthalate, 30 parts by weight of dimethyl isophthalate,
5-sulfoisophthalic acid dimethyl sodium salt 10 parts by weight,
52 parts by weight of ethylene glycol, 16 parts by weight of 1,4-cyclohexanedicarboxylic acid, 5 parts by weight of polyethylene glycol (3,000 in number average molecular weight), 0.05 part by weight of antimony trioxide,
0.13 parts by weight of phosphoric acid trimethyl ester was added, the temperature was gradually raised, the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain an intrinsic viscosity of 0.1.
A water soluble copolyester resin having 52 was obtained.

<< Preparation of In-line Subbing Solution >> The above copolyester resin was prepared to be an 8% (W / W) aqueous solution to obtain a subbing solution.

[0192] << Preparation of Antistatic Subbing Solution a-11 and b-11 >>       Butyl acrylate 30% by weight,       t-butyl acrylate 20% by weight,       Styrene 25% by weight       2-hydroxyethyl acrylate 25% by weight     Copolymer latex liquid (solid content 30%) 540 g     Compound (C-6) 0.6 g     Hardener Hexamethylene-1,6-bisethyleneurea 0.8 g     ASP (I) -7- (a) 300 g     Make up to 1 liter with water.

Antistatic subbing liquids a-11 and b- of the above samples
ASP of the π-electron conductive polymer of the present invention in 11
In place of (I) -7- (a), various A-11 and B containing a dispersion of a π-electron conductive polymer as shown in Table 2 were used.
-11 An undercoated film was prepared.

8 W / m ^{2 on} both sides of the subbing layers A-11 and B-11
The corona discharge treatment for minutes was performed, and A-12 and B-12 were coated on the undercoating upper layer coating liquids a-12 and b-12 so as to have a dry film thickness of 0.08 μm.

[0195] << Preparation of Undercoating Upper Layer Coating Solutions a-12 and b-12 >>     Gelatin 15 g     Compound (C-6) 0.6 g     N, N ', N "-Trisacryloyl-1,3,5-trimethylenetriamine 1.0 g     Silica particles (average particle size 3 μm)   Made up to 1 liter with water.

The following photosensitive layer was coated on the above A-12 and B-12 to prepare a photographic light-sensitive material for silver halide X-rays.

<Preparation of silver halide X-ray photographic film><< Silver halide emulsion formulation >> While controlling at 60 ° C., pH = 8 and pH = 2.0, the average grain size is 0.3 by the double jet method.
A monodisperse cubic emulsion of silver iodobromide containing 2 mol% of silver iodide was obtained. The number of twins in this emulsion was 1% or less from the electron micrograph. The silver halide grains of this emulsion were used as seed crystals (A) and grown as follows.

That is, the seed crystal (A) was dissolved in 8.5 liters of a solution containing gelatin kept at 40 ° C. and, if necessary, ammonia, and the pH was adjusted with acetic acid. Using this solution as a mother liquor, an aqueous 3.2 N ammoniacal silver ion solution was added by the double jet method. In this case, pH and EAg
Was changed at any time depending on the silver iodide content and the crystal habit. That is, pAg was controlled to 7.3 and pH was controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, the pH was changed from 9 to 8 and the pAg was kept at 9.0 to grow up to 95% of the grain size. Then, potassium bromide solution was added with a nozzle for 8 minutes, and pAg was adjusted to 11.
It was dropped to 0, and 3 minutes after the addition of potassium bromide, the mixing was completed. This emulsion has an average grain size of 0.55 μm and the silver iodide content of the entire grain is about 2.2 mol%.

Next, a desalting step was carried out in order to remove an excessive soluble salt of this reaction solution. That is, the reaction solution was kept at 40 ° C., and 5 g of the following compound (1) was added per 1 mol of AgX and MgS.
8 g of O ₄ was added per 1 mol of AgX, and the mixture was stirred for 5 minutes and then allowed to stand. Then, the supernatant was discharged to a liquid volume of 200 ml per mol of AgX. Then, 1.8 liter of pure water at 40 ° C. was added per 1 mol of AgX, and the mixture was stirred for 5 minutes. Then MgS
O ₄ was added per 1 mol of 20 g Agg, and the mixture was left to stir in the same manner as above, the supernatant was removed, and desalting was performed. The solution was then stirred and gelatin was added to redisperse AgX.

[0200]

[Chemical 21]

The resulting emulsion was chemically sensitized as follows. That is, the emulsion was first kept at 55 ° C., and then ammonium thiocyanate, chloroauric acid and hypo were added to perform gold / sulfur sensitization. After sensitization, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added.

Of the above steps, the sensitizing dye was added at the end of each step.

To these emulsions, as additives, 400 mg of t-butyl-catechol per mol of AgX, 1.0 g of polyvinylpyrrolidone (molecular weight 10,000), 2.5 g of sodium polystyrene sulfonate, 10 parts of trimethylolpropane were added.
g, 5 g of diethylene glycol, 50 mg of nitrophenyl-triphenylphosphonium chloride, 4 g of 1,3-dihydroxybenzene-4-sulfonic acid ammonium salt, 15 mg of 2-mercaptobenzimidazole-5-sulfonic acid sodium salt

[0204]

[Chemical formula 22]

10 mg of 1,1-dimethylol-1-bromo-1-nitromethane was added to each to prepare an emulsion coating solution.

The following compounds were added as protective layer additives. (The added amount is shown per 1 g of gelatin.)

[0207]

[Chemical formula 23]

Further, 30% by weight of the compound (L _x -2) was added to the amount of gelatin.

Further, 7 mg of a matting agent made of polymethylmethacrylate having an average particle diameter of 5 μm, 70 mg of colloidal silica having an average particle diameter of 0.013 μm, 8 mg of glyoxal and 6 mg of formaldehyde were added to prepare a coating liquid for a protective layer.

The silver coating amount of each sample was 5 g / m ^{2 on} both sides. The protective layer coating solution was a 3% gelatin solution coated so that the coating gelatin amount including the emulsion layer protective layer was 6.5 g / m ² on both sides. In addition, poly (co-cyclohexyl methacrylate-co-isononyl acrylate-co-glycidyl methacrylate) having a polymer latex average particle diameter of 0.10 μm, which is 30% by weight based on the amount of gelatin, is added.

<Evaluation method> << Scratch Test >> A scratch test was conducted in the same manner as in Example 1.

<< Ash Adhesion Test >> In the same manner as in Example 1, the developed medical photographic film was subjected to an ash adhesion test.

<< Spark Detection Test >> A rubber roller was placed on a rubber plate under the same conditions as in the ash adhesion test of Example 1 in a dark room where the humidity was adjusted to 23 ° C. and 40% RH. The wet unexposed sample was rotated 10 times to generate static electricity, and the sample was developed to evaluate the degree of spark generation. The degree and rank of sparks are shown below.

A: No trace of sparks in the sample area B: Something in the sample area is not clear that seems to be spark C: There is one very small spark trace in the sample area D: Of the sample area Several small spark traces are seen inside E: There are many spark traces in the sample area F: There are spark traces on the entire sample area G: There are spark traces on the entire sample area The test results are shown in Table 2 Show.

[0215]

[Table 2]

<Evaluation and Results> As is clear from Table 2,
When the average particle size and the particle size variation coefficient are within the scope of the present invention,
Excellent charging performance and scratch resistance.

[Example 3] A polyethylene-2,6-naphthalate film as a plastic film coated with a coating composition containing a subbing solution and a π-electron conductive polymer as described below for photography of a plastic film The following silver halide color photographic emulsion was coated on the support to prepare a color film.

<Preparation of polyethylene-2,6-naphthalate support><< Synthesis of polyethylene-2,6-naphthalate resin >> 100 parts by weight of methyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol as an ester exchange catalyst 0.1 part by weight of calcium acetate hydrate was added, and transesterification reaction was carried out according to a conventional method. The product obtained contains antimony trioxide.
0.05 parts by weight and 0.03 parts by weight of phosphoric acid trimethyl ester were added. Then, gradually raise the temperature and reduce the pressure, polymerize under the conditions of 290 ° C and 0.5 mmHg, and obtain an intrinsic viscosity of 0.60 polyethylene-2,6,-
A naphthalate resin was obtained.

<< Preparation of Colored Polyethylene-2,6-Naphthalate Film >> Polyethylene-2,6, -naphthalate resin was mixed with Bayer dyes Macrolex Green G and Macrolex Red 5B at a ratio of 1: 1. An extruder was used to prepare master pellets having a dye concentration of 2000 ppm. A film was produced using the uncolored pellets and the colored pellets obtained as described above.

Non-coloring and coloring were blended in a tumbler type mixer in a weight ratio of 9: 1. Then, after vacuum-drying at 150 ° C. for 8 hours, it was melt-extruded in layers from a T-die at 300 ° C., adhered onto a cooling drum at 50 ° C. while electrostatically applied, and cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The uniaxially stretched film thus obtained was subjected to a total transverse stretching ratio at a first stretching zone of 145 ° C. using a tenter type transverse stretching machine.
50% stretch, and then the total transverse stretch ratio at the second stretch zone 155 ° C
It was stretched so as to be 3.3 times. Then, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at first heat-solidifying zone 200 ° C. for 5 seconds, and second heat-setting zone at 230 ° C. for 15 seconds. Then, while slowly relaxing in the lateral direction by 5%, it is slowly cooled to room temperature over 60 seconds, released from the film clip, rolled up, and the thickness is 80μ.
A biaxially stretched film of m was obtained.

<Formation of Undercoat Layer / Antistatic Layer> Both sides of the polyethylene-2,6-naphthalate film obtained above were subjected to a corona discharge treatment of 8 W / m ² · min, and one surface thereof was undercoated. The coating liquid a-20 is applied to a dry film thickness of 0.8 μm to form an undercoat layer A-20, and a corona discharge treatment of 8 W / m ² · min is further applied on the undercoat layer A-20 to form the undercoat coating liquid a-. 21 to dry film thickness 0.1
It was applied so as to have a thickness of μm to obtain an undercoat layer A-21. Corona discharge was similarly applied to the other surface, and then antistatic coating liquid b-20 was applied so as to have a film thickness of 0.8 μm to obtain antistatic layer B-20.

[0223] <Subbing coating liquid a-20>       Butyl acrylate 30% by weight       t-Butyl acrylate 20% by weight       Styrene 25% by weight       2-hydroxyethyl acrylate 25% by weight     Copolymer latex liquid (solid content 30%) 270 g     Compound (C-6) 0.6 g     Hexamethylene-1,6-bisethyleneurea 0.8 g   Make up to 1 liter with water.

[0224] << Undercoat layer coating liquid a-21 >>     Gelatin 10 g     Compound (C-6) 0.2 g     Compound (C-7) 0.2 g     N, N ′, N ″ -Trisacryloyl-1,3,5-trimethylenetriamine 0.1 g     0.1 g of silica particles with an average particle size of 3 μm     Make up to 1 liter with water.

[0225] <Antistatic subbing coating solution b-20>       Butyl acrylate 40% by weight       Styrene 20% by weight       Glycidyl acrylate 40% by weight     Copolymer latex liquid (solid content 30%) 270 g     Compound (C-6) 0.6 g     Hexamethylene-1,6-bisethyleneurea 0.8 g     ASP (I) -7- (a) 200 g     Make up to 1 liter with water.

The mixed solution was adjusted to pH 7.0 and dispersed by a stirrer and a sand mill to prepare.

The antistatic dispersion of the antistatic subbing coating liquid was applied as shown in Table 4 instead of ASP (I) -7- (a).

Subsequently, a corona discharge of 8 W / m ² · min was applied on the undercoat layer B-20 to apply a magnetic recording layer coating solution c-21 to prepare a magnetic recording layer C-21 layer. .

<Magnetic Recording Layer Coating Solution c-1> Carnauba wax (10 parts by weight) was heated and dissolved in toluene (150 parts by weight), cooled, and then mixed with cyclohexanone (75 parts by weight) and methyl ethyl ketone (150 parts by weight). Cellulose nitrate BTH-1 / 2 100 parts by weight (solid content 70% by weight) and Co-deposited γ-Fe ₂ O ₃ (long axis 0.8 μm, Fe ²⁺ / Fe ³⁺ =
0.2, Hc = 600 oersted) (5 parts by weight), mixed with a dissolver for 1 hour, and then dispersed with a sand mill, c-
It was 21.

A 25 W / m ² · min corona discharge was applied to the A-21 surface of the polyethylene-2,6-naphthalate film which had been subbed, and the following multilayer color photographic constituent layers were sequentially applied to obtain a silver halide color. A photographic light-sensitive material was prepared.

<Coating of Color Photographic Constituent Layer> For silver halide and colloidal silver, the coating amount shown below is the amount expressed in g / m ² unit in terms of metallic silver. For couplers and additives, the amounts are shown in units of g / m ² and for sensitizing dyes, the number is expressed in mol per mol of silver halide in the same layer.
The total weight was adjusted to give a dry film thickness.

<< First Layer: Antihalation Layer >> Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 << Second layer: Intermediate layer >> Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 << Third layer: low-sensitivity red-sensitive layer >> Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD-2) 1.4 × 10
^-4 sensitizing dye (SD-3)
1.4 × 10 ^-5 Sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (Di-1) 0.025 High boiling point solvent (OIL-3) ) 0.48 Gelatin 1.09 << Fourth layer: Medium-sensitive red-sensitive layer >> Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 Sensitizing dye (SD-2) 0.86 × 10 ^-4 Sensitizing dye (SD-3) 1.15 × 10 ^-5 Sensitizing dye (SD-4) 0.86 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 DIR compound (Di-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 << Fifth layer: high-sensitivity red-sensitive layer >> Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 sensitization Dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 << 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 >> Iodine Silver bromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler ( M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 << 8th layer: Intermediate layer >> Gelatin 0.41 << 9th layer: Medium sensitive green-sensitive layer >> Silver iodobromide Emulsion B 0.30 Silver iodobromide Emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-7) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-8) 1.2 × 10 ⁻⁴ Magenta Coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR Things (Di-2) 0.025 DIR compound (Di-3) 0.002 High boiling solvent (OIL-4) 0.12 Gelatin 0.50 iodobromide emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 -5 Sensitizing dye ( SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD-8) 7.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 << 11th layer: Yellow filter layer >> Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 << 12th layer: Low sensitivity blue sensitive layer >> Silver iodobromide emulsion A 0.12 Iodine Silver bromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler ( Y-2) 0.50 DIR compound (Di-4) 0.04 DIR compound (Di-5) 0.02 High boiling point The solvent (OIL-2) 0.42 Gelatin 1.40 "13 layer: high sensitivity blue-sensitive layer" silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10
^-5 sensitizing dye (SD-11) 3.1 x 10
^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 << 14th layer: 1st protective layer >> Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol) %) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 << 15th layer: 2nd protective layer >> Alkali-soluble matting agent (average particle size) 2 μm) 0.15 Matting agent Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of polyvinylpyrrolidone having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and a preservative compound (A) were added.

The emulsions used for the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0234]

[Table 3]

The sample was applied by a multi-slide hopper type coater at the first time, and the first to eighth layers were simultaneously applied, and at the second time, the ninth to 15th layers were simultaneously applied thereon.
The specific photographic speed was ISO420. The structure of each compound used for the preparation of the sample is shown below.

[0236]

[Chemical formula 24]

[0237]

[Chemical 25]

[0238]

[Chemical formula 26]

[0239]

[Chemical 27]

[0240]

[Chemical 28]

[0241]

[Chemical 29]

[0242]

[Chemical 30]

[0243]

[Chemical 31]

[0244]

[Chemical 32]

<Development Processing> A color photographic film sample was developed according to the following formulation and conditions.

[0246] <Processing conditions>     1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃     2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ℃     3. Washing with water 3 minutes 15 seconds 24-41 ℃     4. Stationary 6 minutes 30 seconds 38.0 ± 3.0 ℃     5. Washing with water 3 minutes 15 seconds 24-41 ℃     6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃     7. Dry 50 ° C or less The composition of the treatment liquid used in each step is shown below.

[0247] << color developer prescription >>   4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl)   Aniline / sulfate 4.75g   Anhydrous sodium sulfite 4.25g   Hydroxylamine 1/2 sulfate 2.0g   Anhydrous potassium carbonate 37.5g   Sodium bromide 1.3g   Nitrilotriacetic acid sodium salt (monohydrate) 2.5 g   1.0 g of potassium hydroxide   Add water to make 1 liter (pH = 10.1).

[0248] << Bleaching liquid prescription >>   Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g   Ethylenediaminetetraacetic acid diammonium salt 10.0 g   Ammonium bromide 150.0 g   Glacial acetic acid 10.0g   Add water to make 1 liter, and adjust to pH 6.0 with aqueous ammonia.

[0249] <Fixer formulation>   Ammonium thiosulfate 175.0 g   Anhydrous sodium sulfite 8.5g   Sodium metasulfite 2.3g   Add water to 1 liter and adjust to pH 6.0 with acetic acid.

[0250] 《Stabilizer recipe》   Formalin (37% aqueous solution) 1.5 ml   Conidax (manufactured by Konica Corporation) 7.5 ml   Add water to make 1 liter.

<Evaluation method> << Scratch Test >> A scratch test was conducted in the same manner as in Example 1. << Ash adhesion test >> The same ash adhesion test as in Example 1 was performed.

<< Peel off static test >> 35 samples in a dark room
Cut into a width of 1 mm and a width of 1 mm, adjust the humidity of the film in a dark room environment of 23 ° C. and 80% RH, tape the tip of the film to the core of 10 mm in diameter and 40 mm in length, and apply the photosensitive layer. Wrap it inside, tape the ends, put the wrapped film in a sealed can, and heat it in an oven at 50 ° C for 24 hours.
It was opened and peeled off in a dark room environment of 20 ° C. and 20% RH, and immediately subjected to development processing to examine the degree of color development of the blue sensitive layer due to yellow static electricity. The degree of color development was ranked as follows.

A: No color development B: A slight slight color development is felt in a very small portion C: There are 1 or 2 slightly small color development points in the entire length D: Color development over the entire length Slightly scattered dots E: Coloring points are scattered over the entire length F: Coloring is considerably observed G: Coloring is entirely observed <Evaluation and results>

[0254]

[Table 4]

As can be seen from Table 4, when the average particle diameter and the coefficient of variation of the particle diameter are within the range of the present invention, good results were obtained in both antistatic performance and scratch resistance.

[0256]

By controlling the average particle size and the coefficient of variation of the particle size of the π-electron conductive polymer,
The antistatic performance of the antistatic layer containing the electroconductive polymer particles was improved, and the antistatic layer was less likely to be scratched, and a stable antistatic layer could be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-8-120195 (JP, A) JP-A-6-295016 (JP, A) JP-A-6-263899 (JP, A) JP-A-2- 308160 (JP, A) JP-A-2-282246 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J ^7/ 04-7/06 B32B 27/00-27/42 G03C 1/795 G03C 1/89

Claims (3)

(57) [Claims] 1. A layer comprising a solid dispersed π-electron conductive polymer having an average particle size of 0.1 to 0.5 μm and a coefficient of variation of the particle size of 50% or less. Plastic film to do. 2. The π-electron conductive polymer is polypyrrole and its derivative, polythiophene and its derivative, polyfuran and its derivative, polyaniline and its derivative, poly (2,5-thienylenevinylene) and its derivative, polyisothia. The plastic film according to claim 1, which is at least one of naphthene and its derivative, thiophene and pyrrole copolymer and its derivative, polyparaphenylene vinylene and its derivative, and polyselenophene and its derivative. 3. The silver halide photographic light-sensitive material according to claim 1, which has the plastic film as a photographic support.