JPH08160568A - Antistatic coating composition, plastic film having antistatic layer thereby and silver halide photographic sensitive material treated for antistatic - Google Patents

Abstract

PURPOSE: To provide a plastic film and silver halide photographic sensitive material which stabilize the electrical conductivity of water-based antistatic coating compns. contg. a π electron-based electrically conductive polymer and acceptor.dopant and have excellent antistatic performance. CONSTITUTION: The antistatic coating compns. of an aqueous soln. or moisture- dispersed liq. contg. the electron-based electrically conductive polymer and acceptor.dopant and having a calcium ion concn. of <=500ppm, the plastic film treated for antistatic thereby and the silver halide photographic sensitive material are provided. The antistatic performance is stabilized and made excellent by keeping the concentration of calcium ions in the water-based antistatic coating compns. contg. the π electron-based electrically conductive polymer and acceptor.dopant down to <=500ppm.

Description

Detailed Description of the Invention

[0001]

This invention relates to an antistatic coating composition,
The present invention relates to a plastic film having an antistatic layer coated therewith and an antistatic silver halide photographic material having the plastic film. Specifically, an antistatic coating composition using a π-electron conductive polymer,
The present invention relates to a plastic film having an antistatic layer to which it is applied and a silver halide photographic light-sensitive material having the plastic film.

[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. In particular, a silver halide photographic light-sensitive material having an insulating film support (hereinafter, also referred to as a photographic light-sensitive material) is apt to cause troubles due to electrification during the manufacturing process, transportation in a camera, etc. The accumulated static electricity generated by contact friction with the surface of the substance, peeling, and the like discharges and causes troublesome defects that cannot be detected unless the photographic light-sensitive material is exposed to light and developed.
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 developed various antistatic techniques and 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, so static electricity is generated in low humidity 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 an excellent antistatic property at low humidity, but it is strongly colored, and as described above as another photographic light-sensitive material. The performance is also unsatisfactory, and the above problems have not been solved yet.

[0005]

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.

Since the π-electron conductive polymer does not show good conductivity as it is, it is common to express excellent conductivity by doping the π-electron conductive polymer with a dopant. However, a π-electron conductive polymer is prepared as an antistatic coating composition,
When it was applied to a plastic film and the charging performance was examined, it was found that the conductivity level fluctuated and a stable antistatic layer could not be obtained.

The first object of the present invention is to provide a water-based antistatic coating composition using a π-electron type conductive polymer and having stable conductivity, and an antistatic coating composition with little coloring. A second object is to provide a plastic film having excellent charging performance by coating an antistatic coating composition using a stabilized π-electron conductive polymer on a plastic film. The purpose of is to provide a photographic light-sensitive material having excellent charging performance using a stabilized π-electron conductive polymer.

[0008]

Means for Solving the Problems The present inventors set the calcium ion concentration of an aqueous dispersion or an aqueous solution containing a π-electron conductive polymer and an acceptor dopant (hereinafter simply referred to as a dopant) to 500 ppm or less. As a result, an antistatic coating composition having excellent conductivity and stability was obtained, and the problem was solved by this. Then, by coating this antistatic coating composition on a plastic film, an antistatic plastic film having excellent conductivity and stability is provided, and by providing a silver halide emulsion photosensitive layer on at least one surface of the plastic film, it is stabilized. It was possible to obtain a photographic light-sensitive material having excellent charging performance.

The inventors of the present invention evaluated the charging performance after applying an aqueous dispersion or aqueous solution containing a π-electron conductive polymer to a plastic film, and found that there were many variations. It was found that the degree of contribution of the dopant to the π-electron conductive polymer was different. The relationship between conductivity and dopant concentration of π-electron conductive polymers is known as follows (edited by Naoya Ogata, “Conductive Polymers”, p. 12, Kodansha, 199).
0).

Σ = 10 × y _π ³ where σ is the conductivity (Scm ⁻¹ ) and y _π is the dopant ion concentration per π electron. S is Siemens, which is the reciprocal of Ohm, Ω ^-1 .

However, such a relationship may not be clear in an aqueous dispersion system or an aqueous solution system, and a π-electron conductive polymer is dispersed or dissolved in water and doped with a dopant to form a coating composition. , When I applied it to a plastic film and measured its conductivity, I found that the conductivity level was fluctuating, and it became clear that the conductivity level was considerably dependent on other factors. It was found that the main factor was the concentration of metal ions in water, and the concentration of calcium ions among metal ions was greatly affected. It is not clear why calcium ions hinder the favorable arrangement (homogeneity) of the dopant ions with respect to the π-electron system, but the calcium ions act on the dopant ions to form the dopant ions for the π-electron system polymer. It is presumed that this is to reduce the contribution of. By reducing the calcium ion concentration of the aqueous dispersion or aqueous solution of the antistatic coating composition of the present invention to 500 ppm or less, it is possible not only to stabilize the conductivity level, but also to enhance the conductivity, Even if the coating layer is thin, it has good conductivity and can be made into a thin film. As a result, the coloring peculiar to the π-electron conductive polymer can be reduced, which reduces the sensitivity of the silver halide photographic light-sensitive material. In addition, the color balance in color photography can be improved. Further, when a water-soluble binder such as gelatin is used as the binder of the antistatic layer, the drying property after processing such as development of a color photograph is accelerated and the processing time can be expected to be shortened.

The present invention will be described in detail below.

The π-electron conductive polymer of the present invention means a conjugated system having a molecular skeleton as 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 a single bond. It is a polymer. Examples of these conjugated polymers are 1) aliphatic conjugated system: a polymer in which carbon-carbon conjugated systems such as polyacetylene are alternately long, and 2) aromatic conjugated system: poly (paraphenylene).
Polymers with long conjugation of aromatic hydrocarbons such as, 3) Heterocyclic conjugated systems: Polymers with conjugated heterocyclic compounds such as polypyrrole and polythiophene, 4) Heteroatom-containing conjugates System: Polymer in which an aliphatic or aromatic conjugated system such as polyaniline is bonded with a hetero atom, 5) Mixed conjugated system: Conjugate having a structure in which constituent units of the above conjugated system such as poly (phenylene vinylene) are alternately bonded -Based polymers, 6) Double-chain 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 phthalocyanines or their Polymers having heteroatoms or conjugated bonds between molecules, 8) Conductive composites: polymers obtained by graft copolymerizing the above conjugated polymer chains with saturated polymers, and saturated polymers. Complex and the like obtained by polymerizing the conjugated polymer and the like in Rimmer, but the conjugated polymer can be applied to the present invention as a π electron-based conductive polymer.

The above π-electron 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) include 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 (furanvinylene) and its derivatives, poly (2,2 ′
-Thienylpyrrole) and its derivatives, 6) as polyperinaphthalene, 7) as metal phthalocyanine,
And 8) include 3) polythiophene (including derivatives), polypyrrole (including derivatives), 4) polyaniline (including derivatives), and 5) poly (paraphenylene vinylene) (derivatives thereof). Included), poly (thiophenvinylene) (including its derivatives), and the like, and a π-electron conductive polymer composite of a polymer having a side chain via a connecting group.

Among the above, the heterocyclic conjugated system of 3), 4)
The heteroatom-containing conjugated system of 5), the mixed conjugated system of 5), the conductive composite system of 6), and the conductive composite of 8) are easy to obtain high conductivity, and are preferable as the electronic conductive polymer of the present invention.

Furthermore, among these, the following general formula ASP
(I), ASP (II), ASP (III), ASP (IV) and ASP
A polymer having a repeating unit represented by (V) is particularly preferable in the present invention.

General formula ASP (I)

[0018]

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General formula ASP (II)

[0020]

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General formula ASP (III)

[0022]

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General formula ASP (IV)

[0024]

[Chemical 4]

General formula ASP (V)

[0026]

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In the formula, X is> N-R _X , -S-, -O.
-, - represents _{Se-, 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 sulfo group or a salt thereof, an alkyl group. It represents a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an alkylcarboxyl group or a salt thereof, or a sulfamide group. R _X is each 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 alkylsulfo group or a salt thereof, an alkylcarboxyl group or a salt thereof, an alkylsulfoamide group. And a hydrogen atom is particularly preferable. In addition, 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 and 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 A cyano group, an acyl group, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an alkylsulfo group or a salt thereof, an alkylcarboxyl group or a salt thereof.

Further, R ₁ or R ₂ , R ₃ or R ₄ , R ₅
Or R ₆ , R ₇ or R ₈ , R ₉ or R ₁₀ , R ₁₁ or R ₁₂ , R ₁₃ or R ₁₄ , R ₁₅ or R ₁₆ , and R ₁₇ or R ₁₈ are represented by the general formula ASP (V). As described above, one of them may be bonded to the divalent linking group L that connects the other chain polymer main chain P ₁ and the π-electron conductive polymer A.

Here, P ₁ and P ₂ of the general formula ASP (V) represent a monomer unit forming another chain polymer main chain, and P ₁
Is a monomer unit that forms a polymer main chain and can form a part of the linking group L as a side chain, P ₂ represents a monomer unit that forms a polymer main chain with P ₁ , and L represents a polymer main chain and π electrons. A is a divalent linking group capable of linking with a conductive polymer, and A is a general formula ASP (I), ASP (II), ASP (II
It represents a monomer unit of a π-electron conductive polymer represented by I) and ASP (IV), and is bonded to the main chain by a linking group L.

Examples of the chain polymer of P ₁ and P ₂ are:
Any may be used, for example, vinyl polymers, polyethers, polysulfonamide, polypeptides, polyamides, polyesters, polyureas, polyurethanes, etc., but vinyl polymers are preferred as chain polymers.

As the basic monomer forming the vinyl polymer, acrylic acid, methacrylic acid, esters or amides derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diester Acetone acrylamide, n-butyl methacrylamide, t-butyl methacrylamide, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, is
o-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate,
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate,
n-octyl methacrylate, lauryl methacrylate,
2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate), vinyl ester (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile,
Aromatic vinyl compounds (eg, styrene, and derivatives thereof such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid,
Citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N
-Vinyl pyridine and 2- and 4-vinyl pyridine, etc. are mentioned, but not limited thereto.

Examples of the linking group which forms the linking group L together with P ₁ and A are shown below, but the linking group is not limited thereto.

[0034]

[Chemical 6]

In the general formula ASP (I), the above 3),
5) and 8) are the above 4) and 8) in the general formula ASP (II).
However, in the general formula ASP (III), the above 4) and 8) are
P (IV) contains the above 5) and 8), and general formula ASP (V) contains the above 3), 4), 5) and 8), respectively.

The content of the π-electron conductive polymer in the antistatic coating composition of the present invention is 0.5 to 50% by weight in the composition in order to enhance conductivity when applied as an antistatic layer. It is particularly preferably 1 to 20% by weight.

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.

In the case of the composite polymer having the π-electron type conductive polymer of the present invention as a repeating unit in the side chain,
Of the main chains (P ₁ + P ₂ ) of the composite polymer, a simple main chain polymer (P ₂ ) having no π-electron conductive polymer
The molar ratio P ₂ / (P ₁ + P ₂ ) of may be arbitrary,
It is preferably 20 to 95 mol%.

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 cyclopolymerization, 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.

The method for polymerizing the polymer of the present invention is described in detail in "Electrically Conducting Polymer", edited by Naoya Ogata, pp. 57-93. In addition, more specifically, JP-A-2-255770
No. 2-252726, J, Chem.Soc.Chem.Comm
un., 1983, 854, J.Polym.Sci.Polym.Lett.ed., 18
Volume, p. 9 (1980), J. Chem. Soc. Chem. Commun. 1986, 13
48, Polymer 27, 455 (1986), Synthetic Metal
s, 26, 383 (1988), Polymer Commun., 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 oxidation polymerization method described above, the positive electrode and the negative electrode are immersed or dissolved in water or an organic solvent to dissolve or disperse the monomer and the conductive salt, 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 the catalyst 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.

Examples of the electrode material used in the electrolytic oxidation polymerization method include metal electrodes such as Au, Pt, Ni, Cu, and Sn, carbon electrodes, and 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.

Examples of the conductive salt used in the electrolytic oxidation polymerization method include alkali metal cations such as Li ⁺ , Na ⁺ and K ⁺ , NO ⁺ and N.
O ^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 -, Cl
_{^{O 4 -, AlF 4 -,}} AlF 6 -, NiF 4 2-, ZrF 6 2-, TiF 6 2-, HSO 4 -,
Negative ions such as SO ₄ ²⁻ , Cl ⁻ , Br ⁻ , F ⁻ , I ⁻ and salts thereof, CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , polystyrene Sulfonic acid anions such as sulfonic acid and their salts, HC00L
Examples thereof include salts such as i, 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 the case of 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.

Synthesis of the π-electron conductive polymer composite represented by the above general formula ASP (V) of the present invention is described in JP-A-2-55.
It can be synthesized by the method described in the specification of 770.

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 is one that precipitates at the bottom of the reaction vessel, one that is in a suspended state, one that is in the form of a latex, one that is a transparent solution, and one that is deposited as a film on the electrode. There are various ways of producing such polymers, but they are purified by dialysis, ultrafiltration, washing, etc.
It is preferred to prepare the antistatic coating composition of the present invention. When the π-electron conductive polymer of the present invention is a powder, a mesh is prepared by using a ball mill or the like so that it can be dispersed in the form of fine particles, and the average particle size is 0.05 to 1 μm, preferably 0.1 to 0.5.
After pulverizing to μm, it is preferable to add a dispersant such as a surfactant or a water-soluble polymer to water to disperse the fine particles. As these dispersants, the same dispersants as those used in the above synthesis can be used. When the π-electron conductive polymer is in the form of a latex or a latex, the dispersant is not necessary because it already contains the dispersant, but it may be added if necessary.

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 = La, Ce, P
r, Nd, lanthanides such as Sm), an electrolyte anion ^{(e.g., Cl -, Br -, I} -, ClO 4 -, PF 6 -, AsF 6 -, SbF 6 -, BF 4
^{_{-, CF 3 SO 3 -,}} CF 3 CO 2 -, CH 3 SO 3 -, CH 3 C 6 H 5 SO 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)
Etc. Other _{O 2, XeOF 4, (NO} 2 +) (SbF 6), (NO 2 +) (SbC
^{_{L 6 -), (NO 2}} +) (BF 4 -), FSO 2 OOSO 2 F, AgClO 4, H 2 IrCl 6, L
_{a (NO 3) 3 · 6H} 2 O or the like can be mentioned, but not limited thereto. I ₂ , Br ₂ , HCl, H ₂ SO ₄ , AsF ₅ , Sb
F 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, paratoluenesulfonic acid, polystyrenesulfonic acid and the like are preferably used.

The method of doping the 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 may also be used. Good.

As a method of doping, for example, doping can be carried out with the presence of a dopant in the polymerization field of the π-electron type conductive polymer. Further, a dopant may be added at the time of preparing the antistatic coating composition, but doping at the place of polymerization 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 the same compounds as the dopant of the present invention, and these compounds are synthesized. It is needless to say that the π-electron-type conductive polymer may be doped therein and may serve as a dopant, and thus it is within the scope of the doping of 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.

[0058]

[Chemical 7]

[0059]

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[0060]

[Chemical 9]

[0061]

[Chemical 10]

[0062]

[Chemical 11]

[0063]

[Chemical 12]

[0064]

[Chemical 13]

[0065]

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[0066]

[Chemical 15]

[0067]

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[0068]

[Chemical 17]

(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. The average degree of polymerization of this product was about 1,000 as determined by elemental analysis and NMR.

1-2) Poly (3,4-dimethoxypyrrole)
Synthesis [ASP (I) -6] 3,4-dimethoxy pyrrole 12g, (C ₄ H ₉₎ takes ₄ NBF ₄ 4g and acetonitrile 200 ml, with stirring under a nitrogen atmosphere, to this solution at room temperature, distilled water 70g Fe dissolved in 30ml
The Cl 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 7 and 8 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 NMR
Therefore, the average degree of polymerization was 1,200.

2-2) Synthesis of poly-3,4-diethoxythiophene [ASP (I) -17] 1.5 mol of iron trichloride was added to 1 liter of nitrobenzene and heated to 100 ° C. under nitrogen stream to give 2-chloro-3, 4-diethoxythiophene 0.
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.

2-3) ASP was similarly prepared by the above-mentioned synthesis method.
(I) -11, 12, 13, 14, 15 and 16 were obtained. The average degree of polymerization is described in Chemical formulas 8 and 9 above.

2-4) As for ASP (I) -3 and 26, 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 7 and 11 above.

2-5) For ASP (I) -27 and 28, 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 11 above.

3-1) Synthesis of polythianaphthene [ASP
(I) -18] 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. 2 more
After stirring for an hour, dialysis was performed to obtain an aqueous dispersion of polyisothianaphthene.

The average particle size of the obtained polyisothianaphthene particles was 0.09 μm (Coulter Electronics
(Measured by KK). 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) -20] 5-dodecylbenzo [c] thiophene 3 g and tetramethylammonium chloride 2 g dissolved in 150 ml of acetonitrile were reacted. Electrolyte solution, 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) ASP was similarly performed by the above-mentioned synthesis method.
(I) -19, 21 and 22 were obtained. The average degree of polymerization and the dopant are described in Chemical formulas 4 and 5 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 with 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 Distillation-purified aniline (0.2 mol), LiClO _{4 (} 0.7 mol) and acetonitrile (1,000 ml) were stirred while using a Pt plate for both 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 from elemental analysis and NMR.

4-3) ASP (II) -using the above method
2,3,4,5,6,7,8,9,10 and 11 were synthesized. The average degree of polymerization and the dopant of each of these are described in Chemical formulas 12, 13 and 14 above.

5-1) Poly (paraphenylene vinylene)
Synthesis of [ASP (IV) -1] 0.1 mol of p-xylene dichloride was dissolved in 200 ml of acetone and 0.24 mol of diethyl sulfide was added dropwise at -5 ° C over 1 hour. A 100 ml aqueous solution of sodium hydroxide was added dropwise over 30 minutes to initiate the polymerization, and the reaction was continued while adding 100 ml of water to give a viscous solution. The reaction solution was cast on a stainless steel plate to form a film, water was heated to evaporate, the film was peeled from the stainless steel 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 by elemental analysis and NMR, the product 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] 0.1 mol of 1,4-dichloromethyl-3,6-dimethoxybenzene
It was dissolved in 200 ml of acetone, 0.25 mol of diethyl sulfide was added dropwise at -5 ° C 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 ) Is added to carry out a polymerization reaction, and 3
After a lapse of time, the reaction is continued and neutralized, and further 100m of methanol is added.
l Addition and subsequent reaction followed by washing in a large amount of water to wash, drying and dissolving in tetrahydrofuran, casting on a stainless steel plate and drying, peeling from the plate, 250
A transparent film was obtained by heating in an oven at ℃ for 30 minutes. This film was confirmed to be poly (3,6-dimethoxyparaphenylenevinylene) by elemental analysis and NMR, and the average degree of polymerization 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 formulas 14 and 15 above.

6-1) Synthesis of acrylic polymer having polythiophene as a side chain [ASP (V) -1] 0.15 mol of 2-chloro-4-hydroxyethylthiophene, 0.15 mol of pyridine, and 150 ml of acetonitrile at a temperature of 5 ° C. 0.15 mol of methacryl chloride was added dropwise over 40 minutes with stirring, and after stirring for 1 hour, 300 ml of ethyl acetate and 300 ml of water were added.
After the addition of the above, the ethyl acetate side was extracted, concentrated, and purified with a column to obtain 35 g of 2-chloro-4-thienylmethoxyethyl methacrylate (A).

10 g of (A) as the P ₁ monomer,
30 g of n-butyl acrylate as a monomer of P ₂ , 300 ml of ethyl acetate and 0.8 of 2,2-azobisisobutyronitrile
g was stirred while flowing nitrogen gas into the container and reacted for 5 hours. After removing ethyl acetate under reduced pressure with a rotary concentrator and concentrating, 2-chloro-thiophene (0.1 liter) was added at 100 ° C. under a nitrogen gas flow while adding 1 liter of nitrobenzene and 1.5 mol of FeCl ₃ .6H ₂ O.
5 mol was added dropwise over 1 hour. After dropping, the mixture was stirred at 60 ° C. for 6 hours, and nitrobenzene was concentrated under reduced pressure with a rotary concentrator. To this, 500 ml of ethyl acetate was added, and the compound (B) was extracted by heating and purified by a Sephadex column to obtain 65 g of an acrylic polymer (B) having a compound polythiophene in its side chain.
By means of elemental analysis and NMR of this product, the ratio of (P ₁ ) _x / (P ₂ ) _y of the main chain acrylic polymer was 1 / 30.2. The average degree of polymerization of the side chain polythiophene was 35.

6-2) Synthesis of acrylic polymer having polyaniline as a side chain [ASP (V) -3] 1.5 mol of 2-aminoethyl methacrylate, 1.5 mol of p-chloronitrobenzene and 750 ml of N, N-dimethylacetamide.
The mixture was stirred at 120 ° C. for 2 hours while flowing nitrogen gas. To this, 1500 ml of ethyl acetate was added, the ethyl acetate layer was extracted, concentrated, and added with 1500 ml of methanol, and reduced under hydrogen pressure using a Pd-C catalyst. After removing the Pd-C catalyst, methanol was concentrated with a rotary concentrator and purified with a silica gel column to obtain 2,4-aminophenylaminoethylmethacrylate (C) at 200%.
g was obtained.

(C) (P ₁ component) 10 g, n-butyl methacrylate (P ₂ component) 80 g, ethyl acetate 600 ml and 2,
1.5 g of 2'-azobismethylisobutyrate was stirred at 90 ° C for 5 hours while flowing nitrogen gas. The reaction solution was concentrated with a rotary concentrator and purified with a Sephadex column to obtain 90 g of a copolymer (D).

3 g of (D), 4.5 g of aniline, and LiClO ₄ 19
constant voltage method (3V, 2mA / cm ² ) using Pt plates for both positive and negative electrodes while stirring g and acetonitrile 1300 ml.
Electrolytic polymerization was carried out for 2 hours, and the polymer was deposited on the negative electrode. The precipitated polymer was heated and extracted with methyl ethyl ketone, concentrated with a rotary concentrator, and then purified with a Sephadex column to obtain 30 g of polymer (E). As a result of elemental analysis and NMR analysis of this product, the ratio x / y of (P ₁ ) _x and (P ₂ ) _y of the main chain of the copolymerized polymer was 1 / 17.6, and the side chain polyaniline The average degree of polymerization of was 10.

6-3) ASP (V) -by the above method
2, 4, 5, 6 and 7 were synthesized respectively. The ratio x / y of (P ₁ ) _x and (P ₂ ) _{y in} the main chain of the copolymer, the average degree of polymerization of the π-electron conductive polymer in the side chain and the dopant are shown in Chemical Formulas 15 and 16 above. .

The antistatic coating composition of the present invention is an aqueous dispersion or aqueous solution containing a π-electron conductive polymer and a dopant, and can be easily prepared by a usual method. That is, when the π-electron conductive polymer is a solution, it may be prepared by stirring this solution in water, and when the π-electron conductive polymer is a dispersion liquid, it is stirred and dispersed so as not to be aggregated in water as it is. When the polymer is a solid, it may be prepared by adding a dispersant to water and pulverizing with a ball mill or the like to disperse the polymer.

If necessary, the antistatic coating composition of the present invention may contain a binder useful for forming a layer. 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, hydroxy cellulose, carboxy cellulose,
Methylcellulose, dextrin, polyvinylpyrrolidone, styrene or alkyl acrylate and sodium styrenesulfonate, acrylic acid and its salts, copolymers of acrylamide or sodium 2-acrylamido-2-methylpropanesulfonate, etc., polyacrylamide, polyacrylic acid and sodium, Gelatin, casein, etc. are useful, and among them, gelatin is preferably used.

The amount of the binder in the antistatic composition used in the present invention is 0.5 to 20% by weight based on the composition.
Is preferable to apply, more preferably 1 to 10% by weight
Is.

The calcium ion concentration of the antistatic coating composition of the aqueous dispersion or aqueous solution of the present invention is 500 ppm or less, but it is preferable to enhance stability or conductivity.
It is 100 ppm or less, more preferably 20 ppm or less.

In order to obtain a low-concentration antistatic coating composition of calcium ion of the present invention, the water to be used (for example, well water, ground water, river, water such as water supply or industrial water) can be prepared by a conventional method. For example, it is preferable to decalcify by ion exchange and also by distillation, and to decalcify and ionize substances added to the antistatic coating composition.

A cation exchange resin may be used for ion exchange of the water used, and a strongly acidic cation exchange resin is particularly preferable. The so-called mixed bed method of both cation and anion ion exchange resins is preferable because other unnecessary ions can be removed. Further, when the substance to be added contains calcium ions, it is preferable to use an additive having a low calcium ion content. It should be noted that the water contains magnesium ions in addition to calcium ions as cations, and may impede doping like calcium, and it is preferable to remove magnesium as much as possible simultaneously with calcium ions.

When gelatin is used as a binder in the antistatic coating composition of the present invention, the amount of calcium ions must be taken into consideration. Usually, gelatin is abundant, and some contains about 6,000 ppm of calcium ions, and it may not be preferable to use such gelatin as it is in the present invention. Ordinary photographic alkali-processed ossein gelatin contains approximately 4,000 ppm of calcium ions and can be used as a binder in an antistatic coating composition without being decalcified as it is. It is preferable to use gelatin. Calcium amount 1,
It is more preferable to use gelatin of 000 ppm or less, and further
Gelatin of 400 ppm or less is preferable, and gelatin of 100 ppm or less which is almost decalcified is particularly preferable. As a raw material of gelatin, there are pigskin, calfskin, ossein, etc., and as a treatment method of gelatin, acid treatment,
There is alkali treatment (lime soaking treatment). The types of gelatin include acid-treated pigskin gelatin, acid-treated ossein gelatin, alkali-treated calfskin gelatin, and alkali-treated ossein gelatin, all of which can be used as the antistatic coating composition 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. The ion exchange treatment is preferably performed with a gelatin solution at a temperature of 30 to 60 ° C.

By the way, the calcium ion content in the aqueous dispersion or aqueous solution of the antistatic coating composition of the present invention is measured by an analytical method such as a general chelate method, atomic absorption spectrum measurement method or ion chromatography method. I can.
The calcium concentration in gelatin can be measured by the chelate titration method of the calcium content measuring method described in pages 15 and 24 of the photographic gelatin test method (Pagilly method) 7th edition (1992), pages 15 and 24. It is carried out by a flame-type atomic absorption spectrometer of the described metal analysis method. In addition, recently, a method of measuring by ion chromatography has been used.

The calcium ion content in the present invention can be determined by any method. However, when the composition of the present invention contains a mixture having a carboxylic acid such as gelatin, the calcium ion is adsorbed to those substances. It is difficult to know the content of free calcium ions accurately. The IAG report (1989, p. 426) describes the determination of calcium ion in gelatin by ion chromatography. Adsorbed calcium is also measured by a conventional analysis method (for example, the Paggy method) by the atomic absorption method, which is not preferable as a method for measuring calcium as a free ion. Conversely, in the presence of gelatin, calcium ions are adsorbed and an accurate value cannot be obtained, so it is necessary to remove gelatin from the measurement system. As a method for removing gelatin from the measurement system, a method in which an aqueous solution containing gelatin is combined with centrifugation and ultrafiltration, a method in which gelatin particles are immersed in water at 10 ° C or lower for a long time, and swollen gelatin is filtered, or a virus is used. Filtration membrane (0.05
Although there is a method of passing calcium, etc., calcium ion can be analyzed by an atomic absorption method, a chelate method, or an ion chromatography method even if the filtrate from any method is used. Further, the degree of adsorption of calcium ions on gelatin varies depending on the pH of the aqueous gelatin solution, and the measured value of calcium ions changes. PH higher than the isoelectric point of gelatin
In this case, since the calcium ion is adsorbed by gelatin, the free calcium ion measurement value is small, and at a pH lower than the isoelectric point of gelatin, almost all the calcium ion measurement value is large, and therefore it becomes large.

The calcium ion of the water used in the antistatic coating composition of the aqueous dispersion or aqueous solution of the present invention was measured as follows. 1) Collect 100 g of water in an Erlenmeyer flask with a stopper. 2) Measure cations by ion chromatography using 20 μl. 3) Read the content by the calibration curve.

The calcium ion content of gelatin in the present invention was measured as follows. 1) Gelatin 5
g is precisely weighed and collected in a 200 ml Erlenmeyer flask with a stopper,
Ultrapure water (18 μΩ or more) that has been cooled to 10 ° C or less in advance 10
Add 0 ml, stir well, and leave in the refrigerator at 10 ° C or lower. 2) After left in the refrigerator for 1 hour, the gelatin swelled sufficiently, and then again stirred well and left in the refrigerator again.
3) After 17 hours, the solid-liquid is separated using No. 2 filter paper.
4) Using 20 μl of the separated liquid component, the cation is measured by the ion chromatography method. 5) Read the content by the calibration curve. In addition, more preferable results can be obtained by passing the filtrate through a virus filtration membrane after filtering in 3) and using the filtrate for measurement.

The calcium ion in the antistatic coating composition of the present invention was measured as follows. 1) The composition liquid
Collect 100 g in a stoppered Erlenmeyer flask, cool to 10 ° C or less, stir well, and leave in a refrigerator at 10 ° C or less. 2) After standing for 17 hours, use a No. 2 filter paper to separate the solid and liquid. 3) Further pass the filtrate through a virus filtration membrane. 4) Using 20 ml of the separated liquid, the cation is measured by the ion chromatography method. 5) Read the content by the calibration curve.

The conditions of the ion chromatography used for the measurement of calcium ion in the present invention are as follows: Liquid chromatography pump is Hitachi liquid chromatography pump L-6200; Column oven is GL Science LC-Column oven Mode l554;
The column is a column for ion chromatography Hitachi # 271
0; Detector is conductivity detector is Hitachi L-3720; Column temperature is 40
℃; eluent is hydrochloric acid 27.5 mmol, 2-3 diaminopropionic acid monohydrochloride 2.25 mmol, L-histidine monohydrochloride (monohydrate) 2.25 mmol; eluent flow rate 1.0 ml / min; sample injection volume 20 μl .

The calcium ion content was measured without adjusting the pH of the antistatic coating composition. When the composition has an additive having a carboxylic acid such as gelatin, since calcium ions are adsorbed by the carboxylic acid, the pH is adjusted to 5 or less, preferably 4.0 and the total calcium ions are used as a reference value. It is preferable to measure.

The antistatic coating composition of the present invention may contain other water-insoluble polymer. 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.) or a homo or copolymer latex, or other urethane resin dispersion, polyethylene resin dispersion, etc. Is mentioned. 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 an amount of 0.5 to 20% by weight based on the antistatic coating composition.

Various additives may be added to the antistatic coating composition of the present invention. For example, a hardener,
Surface tension adjusting agents, matting agents 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 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. The insolubilization of gelatin is achieved by adding a hardening agent for gelatin to the composition. Examples of the hardener include epoxy-based, aldehyde-based, acryloyl-based, ethyleneimine-based, vinylsulfone-based, and active halogen-based hardeners, which are useful. It is not limited to the following compounds.

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[0112]

[Chemical 19]

<Antistatic Plastic Film>
The antistatic plastic film of the present invention can be obtained by applying the antistatic coating composition of the present invention to a plastic film.

<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 structures of polyester, polycarbonate, polyamide, polyimide, polyphenyl sulfone, polyphenyl ether, cellulose triacetate, polyethylene, polypropylene, polyethylene laminated films and the like are mentioned, but not limited thereto.
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 Films of structured polyester, polycarbonate, cellulose triacetate, polyethylene laminated paper and the like are preferred.

Cellulose triacetate film is mainly used for color photographic film and is widely used. The cellulose triacetate film is prepared by dissolving cellulose triacetate as a raw material in methylene chloride to form a viscous solution, which is extruded from a die to a predetermined thickness on an endless stainless steel belt and dried on a belt, and the belt makes 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, polyethylene naphthalate film, modified polyester film,
Proposals have been made to apply a polycarbonate film or the like to a new photographic film.

Polyethylene terephthalate film and polyethylene naphthalate, especially polyethylene-2,6-naphthalate can be prepared by a conventional polyester method, 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 make resin chips and films by the same standard method as polyethylene terephthalate. In addition, the laminated polyester film includes 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 modified polyester and laminated polyester films 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 is terephthalic acid, 2,6-naphthalenedicarboxylic acid, other naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids containing a metal sulfonate group, aromatic dicarboxylic acids such as isophthalic acid, or these aromatic dicarboxylic acids and C ₁ -C ₄ alcohols or C ₂
A glycol dihalf ester with C ₁₀ ; adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid or these aliphatic dicarboxylic acids and C _{1 to} C ₄ alcohols or C ₂ to
Di half ester with C ₁₀ ; polyether dicarboxylic acid such as polyethylene oxide dicarboxylic acid and polypropylene oxide dicarboxylic acid; or acid component such as C _{1 to} C ₈ alcohol or C _{2 to} C ₁₀ diester; and ethylene glycol, propylene Glycols such as glycol, butanediol, neopentyl glycol, p-xylidene glycol, 1,4-cyclohexanedimethanol; diethylene glycol, triethylene glycol,
Polyethylene glycol, polypropylene glycol,
Polyethylene oxide-polypropylene oxide Copolymer glycol, etc. Polyolefin oxide Consists of ester or polyester component with glycol component such as glycols.

As the metal sulfoaromatic dicarboxylic acid as a 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 20 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%.

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As the polyalkylene glycols useful as a modifying component of the modified polyester, polyethylene glycol is preferable, and the molecular weight thereof is not particularly limited, but preferably 300 to 100,000, more preferably 600 to 10
000, particularly preferably 1,000 to 5,000. The content of the modified polyester of polyalkylene glycol is preferably 3 to 10% by weight, preferably 4 to 10% by weight based on the total weight of the polyester.
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. 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 ¹ OOCCH ₂ — (OCH ₂ CH ₂ ) _n —OCH ₂ COOR ² Here, R ¹ and R ² are hydrogen or an alkyl group having 1 to 8 carbon atoms, and n 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 intrinsic viscosity of the modified polyester resin useful in the present invention is 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 is useful to have at least one layer of the modified polyester film described above. In the case of three or more layers, the modified polyester layer is an inner layer of the laminated constitution. May also be in the outer layer, but is preferably in the inner layer. This laminated plastic film is preferable in that it does not tend to have a curl as a film, especially as a photographic film.

Examples of the resin layer component 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, and polyimide. 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.

A 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. You can Also, while observing the film under a microscope, scrape each layer, or scrape the film up to half to obtain the analytes of each of the upper and lower layers, and perform hydrolysis to perform liquid chromatography, NMR. It may be measured with 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. It is possible to measure IR (infrared spectroscopic instrument) etc. by mixing with X-ray spectroscopic instrument or KBr, etc., and as a result, it is asymmetrical in terms of absolute amount or peak position of the measurement result corresponding to it, intensity difference, etc. 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 a modifying component in advance in the form of an ethylene glycol diester (more specifically, an 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) pp. 187-286.

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, carbonates and the like 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. Then, melt polymerization may be carried out after transesterification, or a known synthesis method such as solid phase polymerization of a resin obtained by melt polymerization may be employed.

Examples of the catalyst used for polymerization of polyester (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-tacking agent, a softening agent, a fluidity imparting agent, etc. 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 layers or more, and such a resin layer is combined to form a laminated film of two layers. Explaining with an example, it can be manufactured as follows. That is, for example, two kinds of resins are dried by two different vacuum dryers, the respective resins are put into two different extruders, and melt-extruded, and then the respective melted resins are vertically placed in one conduit. In the conduit, two layers of molten resin form a laminar flow and are extruded from the extrusion die having one slit onto the cooling drum to form one unstretched sheet. Alternatively, as another method, Introducing two types of molten polymer into one die, from an extrusion die with two slits, or from an extrusion die that allows two slits to be combined into one slit in the die. The two laminar flow layers were extruded onto 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 a 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 two 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.

In addition to this, there is a method of laminating and laminating separately formed films. That is, two kinds of resins are separately formed into unstretched films or uniaxially stretched films, which are coated with an anchor agent, an adhesive, etc., and the two 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 by 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 application of these antistatic plastic films coated with an antistatic coating composition can be broadly used for drawing films, OHP films, marking films, animation films, etc., in addition to photographic films.

<Undercoat Layer> When the plastic film used in the present invention is used as a film support, a functional layer such as an antistatic layer and a photosensitive emulsion layer of a photographic film are provided on the film support. Therefore, a subbing treatment is performed in advance for the purpose of improving their coatability and maintaining their strong adhesiveness to the film 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 film supports is employed. As the soluble or swellable solvent, acetone,
Examples thereof include, but are not limited to, methylene chloride, ethylene chloride, methanol, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoacetate and dimethylformamide.

Since the undercoating method of the above-mentioned polyester film useful in the present invention can be applied by the polyethylene terephthalate undercoating method, 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, JP-B-52-48312, Belgian Patent Nos. 721,469, 742,769, etc., or a vinylhalogenoester-containing copolymer or a vinylhalogenoester-containing copolymer and vinyl chloride and / or vinylidene chloride. Copolymer Contained, Japanese Patent Publication 58-58661, Japanese Patent Publication
58-55497, copolymers containing diolefins as a monomer described in JP-A-52-108114, acrylic polymers described in JP-A-61-204242 and 61-204241, JP-B-5
7-971, JP 61-204240, JP 60-248231, JP 3-2
Examples thereof include the polyester-based polymers described in 65624 and the like.

The undercoating after the biaxially stretched heat setting is applied by undercoating with an organic solvent, or a so-called etching solvent (eg, phenol, cresol, resorcinol, or oxidizer) that 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,
The methods described in JP-A-55-67745 and JP-A-59-19941
n-Butylmethacrylate: A quaternary copolymer latex consisting of t-butylmethacrylate, styrene and 2-hydroxyethylmethacrylate, a surface-active agent, and a water-based undercoating liquid consisting of a curing agent are applied and dried, followed by corona discharge treatment again. Then, a photographic emulsion layer side is provided with an aqueous gelatin solution such as an antihalation layer or an emulsion layer to obtain a light-sensitive material having good adhesiveness. In addition, after the same treatment or undercoat layer is applied to the antistatic layer side on the opposite side,
It is possible to finish a desired photographic light-sensitive material by directly applying an antistatic composition or a binder for an antistatic layer such as cellulose diacetate and then applying the antistatic coating composition as an organic solvent-based liquid. it can.

<Antistatic Layer of the Present Invention> The antistatic layer of the π-electron conductive polymer / dopant of the present invention may or may not have an undercoat layer on the plastic film, but it may be directly or indirectly. It can be obtained by applying the antistatic coating composition of the present invention to. The antistatic layer may be the uppermost layer or an upper layer such as a protective layer may be provided on the antistatic layer. Further, it may be above, between, or below the photographic photosensitive layer. The undercoat liquid and the antistatic coating composition 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. U.S. Pat.No. 3,508,847,
No. 2,941,898, No. 3,526,528, etc., two or more layers may be coated simultaneously, 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 composition of the present invention is preferably 0.0001 to 2 g / m ² in order to obtain a good antistatic performance, and particularly preferably 0.
It is preferably from 001 to 1 g / m ² .

<Back Layer> A layer provided on the opposite side of the photosensitive material having the photosensitive layer on one side of the film 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. Other hydrophilic polymers in this gelatin back layer, if desired
A matting agent, a slip agent, a surfactant, a hardener, a dye, a thickener, a polymer latex, the above antistatic agent and the like can be added.

<Photosensitive layer such as silver halide emulsion layer> As the silver halide photosensitive material according to the present invention, an ordinary black and white photographic light sensitive material (for example, black and white photographic light sensitive material for photography, photographic light sensitive material for printing, X-ray photography) 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, such as 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 IH Positive (including internal fog grains) 〃 〃 Mixed emulsion 995 IJ Item Desalting 995 II-A Item 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. Has 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 additives used can be added by the dispersion method described in RD308119XIV.

For the color light-sensitive material, the above-mentioned RD308119 VII-K is used.
An auxiliary layer such as a filter layer or an intermediate layer described in the section can be provided. Further, various layer structures such as the forward layer, the reverse layer and the unit structure described in the above-mentioned RD308119 VII-K 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 fine ferromagnetic 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 shooting conditions. KAISHO 50-62627 publication, JP 49-4503 publication,
U.S. Pat. Nos. 3,243,376 and 3,220,843, etc., and a transparent magnetic recording on the back surface of a photographic light-sensitive material with the required transparency by selecting the amount and size of magnetic particles. Providing layers is described in U.S. Pat. No. 3,782,947.
No. 4,279,945, No. 4,302,523, and the like. Also, US Pat. No. 4,947,196 and WO90 / 04254 describe a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material that enables magnetic recording on the back surface of the photographic film. Has been done.

As described above, in the silver halide photographic light-sensitive material, for example, various information relating to the photographic light-sensitive material such as the type and manufacturing number of the photographic light-sensitive material, the manufacturer name, the emulsion No.
For example, shooting date / time, aperture, exposure time, lighting conditions, filter used, weather, size of shooting frame, model of camera,
Various information at the time of camera shooting such as use of anamorphic lens, for example, number of prints, selection of filter,
Various information necessary for printing such as customer's color preference, trimming frame size, etc., such as the number of prints, filter selection, customer's color preference, trimming frame size, etc. It is convenient to input the information and other customer information in order to record the above-mentioned matters from the viewpoint of management, improvement of print quality, and efficiency of print work.

In the conventional photographic light-sensitive material, it is impossible to input all the information, and
At the time of shooting, I was only optically entering information such as the shooting date / time, aperture, and exposure time. 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 system is easy to record / reproduce, the use of the magnetic recording system for inputting the above various information to the photographic light-sensitive material has been studied and various techniques have been proposed as described above. There is.

By providing these magnetic recording layers, it becomes possible to record the above-mentioned various kinds of information in the photographic light-sensitive material, which has been difficult in the past, and further, it is possible to record voice and image signals. are doing.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-deposited iron oxide magnetic powder, chromium dioxide magnetic powder, and barium ferrite magnetic powder 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.

[0173]

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 An antistatic plastic film was prepared by applying the antistatic coating composition of the present invention to the following plastic film and subjected to the test.

<Plastic film> A biaxially stretched and heat-fixed polyethylene terephthalate film having a thickness of 100 μm (indicated as PET as a support in Tables 1 and 2), a polyethylene-2,6-naphthalate film also having a thickness of 80 μm (Indicated as PEN for the support in Tables 1 and 2), and thickness 9
A 3-layer laminated film of 0 μm of the following modified polyester and polyethylene terephthalate (indicated as P / M / P as a support in Tables 1 and 2) 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
0.1 part by weight of calcium acetate hydrate was added to 100 parts by weight and 64 parts by weight of ethylene glycol, 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 acid content), polyethylene glycol (number average molecular weight 3000).
8.1 parts by weight (7% by weight of polymer), antimony trioxide
0.05 parts by weight and 0.13 parts by weight of phosphoric acid trimethyl ester were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a modified polyester resin having an intrinsic viscosity of 0.57.

<< Preparation of 3-Layer Laminated Film >> The modified polyester resin (abbreviated as M in Table 1) and commercially available intrinsic viscosity
0.65 polyethylene terephthalate resin (also abbreviated as P) was vacuum dried separately at 150 ° C. and then three extruders (two polyethylene terephthalate resin and one modified polyester resin) were used at 285 ° C. Melt extrusion is performed so that the three layers have a modified polyester as the core of the middle layer, and polyethylene terephthalate is provided on the outer layers on both sides of the core, and the thickness ratio of each layer (P.
/ M / P) is 3/10/7 and the amount is adjusted so that the total film thickness of the finished product is 100 μm, the layers are joined in a T-die and extruded, and then cooled by the electrostatic adhesion method. On the drum,
While being in close contact with each other, it was rapidly cooled and solidified to obtain a laminated unstretched sheet. Then, it was stretched 3.5 times in the machine direction at 85 ° C. Then 95 ° C
Then, the film was stretched 3.5 times in the transverse direction and heat-set at 210 ° C. to obtain a biaxially stretched laminated film.

<Formation of subbing layer> Both surfaces of each film were subjected to corona discharge treatment of 8 W / m ² · min, and one surface was coated with the following subbing coating solution a-1 to a dry film thickness of 0.8 μm. Coating was carried out to obtain an undercoat layer A-1. 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.

<< Undercoating Liquid a-1 >> 30% by weight butyl acrylate 20% by weight t-butyl acrylate 25% by weight styrene 25% by weight 2-hydroxyethyl acrylate Copolymer latex liquid (solid content 30%) 270 g Compound (C-6) 0.6g Hexamethylene-1,6-bisethyleneurea 0.8g Make up to 1 liter with water.

<< Undercoating Liquid b-1 >> 40% by weight butyl acrylate 20% by weight styrene 40% by weight glycidyl acrylate Copolymer latex liquid (solid content 30%) 270 g Compound (C-6) 0.6 g Hexamethylene- 0.8 g of 1,6-bisethyleneurea Make up to 1 liter with water.

Then, 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 antistatic layer B-2 layer and an undercoat layer A-2 layer, respectively, to obtain an antistatic and undercoated plastic film, respectively.

<< Coating Liquid b-2 (Coating Composition for Antistatic) >> Alkali-treated ossein gelatin (Ca ²⁺ content in gelatin is 3,000 ppm, 2,000 ppm, 1,000 ppm, 200 ppm, 20 ppm) 20 g π-electron conductive polymer component (see Tables 1 and 2) Weight to be 100 mg / m ² Compound (C-6) 0.2 g Compound (C-7) 0.2 g N, N ′, N ″ -trisacryloyl-1, 3,5-trimethylenetriamine 0.1g Silica particles with average particle size 3μm 0.1g Water (Ca ²⁺ concentration: 1500ppm, 200ppm, 50ppm, 10ppm, 0ppm
Of water was optionally used) and the Ca ²⁺ concentration of the antistatic coating composition was adjusted as shown in Tables 1 and 2.
Among these waters, water having a Ca ²⁺ concentration of 10 ppm or less was ion-exchanged with a cation exchange resin.

<< 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 having an average particle size of 3 μm.

[0185]

[Chemical 21]

<Evaluation of Antistatic Performance> Two pieces of the film with subbing and antistatic processing were cut into 10 cm square pieces, one piece of which was 23 pieces.
Place in the atmosphere of ℃, 40% RH, and soak the other in water at 20 ℃ for 10 minutes, then put it between filter papers and lightly remove the water.
The sample was dried in an RH atmosphere, conditioned under the same conditions, and subjected to a test.

<< Ash adhesion test >> Under the same conditions as above, a plastic film sample was placed on a rubber plate with the side without the antistatic layer facing up, and the side was charged by rotating the rubber roller 10 times. After 1 minute, the cigarette ash prepared separately was densely and evenly spread over the paper, and the sample (with the antistatic surface facing up) was grasped at both ends with an insulating substance clip in the upper space, which was vertically spread. Use an insulating worm gear to position the sample surface parallel to the plane of the ash and lower it in parallel using a simple device to approach the ash and evaluate the degree of ash adhesion to the sample to check the antistatic effect. It was 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: Level at which no adhesion occurs even when the sample is contacted with ash.

B: When the sample is contacted with ash, the ash adheres to the sample, but when the distance between the sample and ash is 1 cm, the ash does not adhere at all.

C: A level where ash adheres when the distance between the sample and ash is 1 cm, but does not adhere when the distance is 2 cm.

D: Ashes are attached at a distance of 2 cm between the sample and ash, but not attached at a distance of 4 cm.

E: A level at which the ash adheres when the distance between the sample and the ash is 4 cm, but does not adhere at a distance of 6 cm.

F: Ash adheres even when the distance between the sample and ash is 6 cm, but does not adhere at a distance of 8 cm.

G: Ash adheres even if the distance between the sample and ash is 8 cm, but does not adhere at a distance of 10 cm.

H: Level at which ash adheres even if the distance between the sample and ash is 10 cm or more.

[0196]

[Table 1]

[0197]

[Table 2]

<Evaluation and Results> As shown in Tables 1 and 2, if the calcium ion concentration of the antistatic coating composition is high, the ash tends to adhere even if there is a distance between the ash and the film, and the calcium ion concentration is high. It turns out that there is a difference. It was also found that the ash adhesion height changed in the order of calcium ion concentration. In particular, excellent antistatic performance was obtained from an antistatic coating composition having a calcium ion concentration of 500 ppm or less. The antistatic coating composition having a low calcium ion concentration had stable antistatic performance even after repeated adjustments. Also, there was no difference between the plastic films (support).

Example 2 The three types of undercoating and antistatic plastic films used in Example 1 were used as photographic supports, and the undercoating layer A-2 and the antistatic layer B-2 were coated on both sides. 25 W / m ² · min of corona discharge, antistatic layer B-
The following back layer coating solution b-3 and back layer protective layer coating solution b-4 were each coated on top of No. ² with a gelatin amount of 2.0 g / m ^2.
And a back layer B-4 by simultaneous double-layer coating of 1.5 g / m ² . On the other hand, the undercoat layer A-2 was coated with the following emulsion layer coating solution formulation to form an emulsion layer (coating gelatin amount 2.0 g /
m ² ), and an emulsion protective layer (coated gelatin amount 1.
0 g / m ² ), each of which is coated in two layers at the same time and dried,
A photographic light-sensitive material for silver halide printing was prepared and tested.

<Formation of Back Layer and Photosensitive Layer><< Preparation of Back Layer Coating Liquid b-3 >> 36 g of gelatin was swelled in water, heated and dissolved, and then compound (C-1) was used as a dye.
1.6 g, compound (C-2) 310 mg, compound (C-3) 1.9
g, and the compound (N) 2.9 g was added thereto as an aqueous solution, then saponin 20% aqueous solution 11 ml, compound (L _x -
5 g of 1) was added, and 63 mg of compound (C-4) was further added as a methanol solution. To this solution, 800 g of sodium polystyrene sulfonate water-soluble polymer was added as a thickening agent 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 144 mg was added, and water was added to make 960 ml to prepare coating solution b-3 for back layer.

[0201]

[Chemical formula 22]

[0202]

[Chemical formula 23]

<< 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, 3.4 g of sodium chloride, 1.1 g of glyoxal and 540 mg each of mucochloric acid were added. Further, 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, and water was added to make 1 liter to prepare a coating liquid b-4 for a protective film layer.

<< 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 per gram and an aqueous solution of silver nitrate were simultaneously mixed in an aqueous gelatin solution at 40 ° C. for 25 minutes with stirring to obtain 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 liquid 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.

[0209]

[Chemical formula 24]

[0210]

[Chemical 25]

Each of the obtained samples was exposed to white light through a step wedge for measuring sensitometry, and then subjected to processing such as development described below.

<Development processing> <Developer formulation> (Development composition A) Water 150 ml Ethylenediaminetetraacetic acid disodium 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 30mg Potassium hydroxide Amount to bring the pH of the solution to 10.9 Potassium bromide 4.5g (Development composition B) Water 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% W / W aqueous solution) 0.3ml 5- Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer 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 / 3-hydrate 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 sulphate (Al ₂ O ₃ converted content is 8.1% W / W aqueous solution) 26.5 g Fixing When the 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 make 1 liter. The pH of this fixer was about 4.3. The W / W represents weight / weight, and W / V represents weight / volume.

Antistatic performance was evaluated for each of the developed samples. Table 2 shows the results.

<Evaluation of Antistatic Performance><< Ash Adhesion Test >> An exposed and developed sample is placed on a rubber plate with the emulsion side facing up, and the emulsion side is placed on a rubber roller 10
It was rotated and charged. Separately prepared tobacco ash is densely and evenly spread on a paper, and the sample (with the emulsion surface facing downward) is brought close to it, and the degree of ash adhesion to the sample is evaluated in the same manner as in Example 1 to prevent static electricity. I saw the effect.

[0216]

[Table 3]

[0219]

[Table 4]

<Evaluation and Results> As shown in Tables 3 and 4, the antistatic coating composition having a high calcium ion concentration easily adheres to the ash even if there is a distance between the ash and the film. It turns out that there is a difference. It was also found that the ash adhesion height was changed in the order of the calcium ion concentration, and especially those having an ash adhesion of 500 ppm or less had excellent antistatic performance. Also, there was no difference between the plastic films (support).

Example 3 In the process of forming a polyethylene terephthalate film, both sides were subjected to in-line subbing, and medical X-ray photographic emulsion layers were coated on both sides to give a silver halide X-ray photographic light-sensitive material. It was prepared and used for the test.

<Preparation of Polyethylene Terephthalate Film and Formation of Subbing 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 the moisture was blocked. Maintain 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.

<< Undercoat Solution and Antistatic Coating Composition >><< In-Line Undercoat Solution a-10 and b-10 Formulation >> The following modified copolyester was synthesized and dissolved in water to obtain an undercoat solution.

<< Synthesis of Modified 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 performed at 280 ° C. and 0.5 mmHg to obtain an intrinsic viscosity of 0.1.
A water soluble modified copolyester resin having 52 was obtained.

<< Preparation of In-line Subtraction Liquid >> The modified copolyester resin was adjusted to be an 8% (W / W) aqueous solution. << Preparation of subbing liquids a-11 and b-11 >> Copolymer latex liquid of butyl acrylate 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight and 2-hydroxyethyl acrylate 25% by weight (solid content 30 %) 270 g Compound (C-6) 0.6 g Hardener Hexamethylene-1,6-bisethylene urea 0.8 g Make up to 1 liter with water.

8 W / m ^{2 on} both sides of the subbing layers A-11 and B-11
The corona discharge treatment for minutes was applied, and the following antistatic coating compositions a-12 and b-12 were coated on the antistatic layers A-12 and B-12 so that the dry film thickness was 0.08 μm. .

<< Preparation of Antistatic Coating Compositions a-12 and b-12 >> Alkali-treated ossein gelatin (Ca ²⁺ content of 3,000 ppm, 2,000 ppm, 1,000 ppm, 200 ppm, 20 ppm is arbitrarily used) 20 g π Electronic conductive polymer component (see Tables 5, 6, and 7) Weight to be 100 mg / m ² Compound (C-6) 0.6 g N, N ′, N ″ -trisacryloyl-1,3,5-trimethylenetriamine 0.8 g of water (Ca ²⁺ concentration: 800 ppm, 100 ppm, 20 ppm, 0 ppm water was optionally used) was added to make up 1 liter, and the Ca ²⁺ concentration of the composition was adjusted as shown in Tables 5, 6 and 7. Of these water, those having 10 ppm or less were ion-exchanged with a cation exchange resin.

The following photosensitive layer was coated on the antistatic layers A-12 and B-12 to prepare a silver halide X-ray photographic photosensitive material.

<Preparation of photographic film for silver halide X-rays><< Silver halide emulsion formulation >> While controlling at 60 ° C., pAg = 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 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 according to 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 20 g of Ag × 1 mol, and the mixture was allowed to stand with stirring in the same manner as above, the supernatant was removed, and desalting was carried out. The solution was then stirred and gelatin was added to redisperse AgX.

[0230]

[Chemical formula 26]

The resulting emulsion was subjected to the following chemical sensitization. That is, the emulsion was first kept at 55 ° C. 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.

A sensitizing dye was added at the end of each of the above steps.

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

[0234]

[Chemical 27]

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.)

[0237]

[Chemical 28]

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.

For each of the obtained samples, the following two tests (1) and (2) were conducted.

(1) Ash adhesion test: Ash adhesion test of the developed film as in Example 2 (2) Spark detection test: carried out in a dark room where the humidity was adjusted to 23 ° C. and 40% RH In the same manner as in Example 2, a rubber roller was placed on a rubber plate, and the sample was exposed to static electricity for 10 rotations on an unexposed sample that had been conditioned under the same conditions. The degree of spark trace generation and rank are shown below by the method of observing.

There are no traces of sparks in the sample area Rank A There is something that is not clear as a spark in the sample area B There is one very small spark trace in the sample area C Small spark in the sample area Several traces are seen. D: There are considerable spark traces in the sample area. E: There are spark traces in the entire sample area. F: There are spark traces so that the sample surface becomes completely black. G Note that the above sample was developed by SRX-501 automatically. Developing machine (Konica
Processed for 45 seconds with XD-SR developer.

The test results are shown in Tables 5, 6 and 7.

[0245]

[Table 5]

[0246]

[Table 6]

[0247]

[Table 7]

As is clear from Tables 5, 6 and 7, it was found that the antistatic property was improved by lowering the calcium ion concentration of the antistatic composition. Especially 500p
Good results were obtained below pm. The antistatic coating composition of the present invention having a low calcium ion concentration was prepared repeatedly, and all showed stable antistatic performance.

Example 4 Cellulose triacetate film and polyethylene-2,6 as plastic film
-A naphthalate film is coated with the following silver halide color photographic emulsion or the like using both plastic films coated with an undercoat liquid and an antistatic coating composition as described below,
I made a color film.

<Formation of Cellulose Triacetate Film and Processing of Coating Liquid> Commercially available photographic grade cellulose triacetate (TAC) flakes were dissolved in methylene chloride to a concentration of 20%, and triphenyl phosphate was used as a plasticizer. A viscous liquid is prepared by adding it to a concentration of 1% and extruded from an extrusion die onto a stainless steel belt to give a viscous film having a thickness after drying of 90 μm. The film forming machine and the drying process are as follows.

That is, a stainless belt whose surface is polished to a super-glossy surface is stretched over two drums which are separated from each other, and hot water of 40 ° C. is directly applied to the back surface of the upper stainless belt to heat it. The viscous liquid is dried by applying warm air of 60 ° C from the lower back side. The viscous film dries as the belt progresses, and semi-dry TAC
The film becomes a film, and the solid content concentration becomes about 50% in one round of the belt. It is peeled off from the belt, and the film is dried through a group of rotating rolls. An antistatic coating composition is applied, and most of the solvent is removed to obtain a TAC film which has been subjected to undercoating and antistatic treatment. At this time, the subbing liquids a-20 and b-20 were applied on both sides to give a dry film thickness of 0.1 μm, and the belt surface side (emulsion coating side) was used as the subbing layer A-20.
The anti-belt surface side (back surface side) was used as the undercoat layer B-20. Then, the following antistatic coating composition b-21 was applied onto the undercoat layer B-20 on the opposite belt surface so that the dry film thickness would be 0.1 μm.
The antistatic layer was B-21.

<< Subbing liquid a-20 and b-20 >> Polyvinyl acetate-co-maleic anhydride 4.3 g Acetone 640 g Ethyl acetate 135 g Isopropyl alcohol 40 g Colloidal silica 0.2 g << Antistatic coating composition b-21 >> Alkali Treated gelatin (Ca ²⁺ content 3,000ppm, 2,000ppm, 1,000ppm, 200ppm, 20ppm are optionally used) 20g π-electron conductive polymer component (see Tables 9, 10 and 11) Weight compound to be 100mg / m ² (C-6) 0.2 g Compound (C-7) 0.2 g N, N ′, N ″ -trisacryloyl-1,3,5-trimethylenetriamine 0.1 g Silica particles with an average particle size of 3 μm 0.1 g Water (Ca ^{2 +} Concentration: 1500ppm, 650ppm, 150ppm, 20ppm, 0pp
m of water is optionally used) to make 1 liter, and the composition of C
The a ²⁺ concentration was prepared as in Tables 9, 10 and 11. For water of 10 ppm or less, use water that has undergone ion exchange with a cation exchange resin.

<Preparation of polyethylene-2,6-naphthalate support> A commercially available polyethylene-2,6-naphthalate film having a thickness of 75 μm was subjected to a corona discharge treatment of 8 W / (m ² · min) on both sides, The undercoating coating solution a-30 on the surface of the
to form a subbing layer A-30, which is further subjected to a corona discharge treatment of 8 W / (m ² · min) to apply the subbing coating solution a-31 to a dry film thickness of 0.1 μm. It was applied so as to form an undercoat layer A-31. Further, after corona discharge was similarly applied to the other surface, the antistatic coating composition b-30 having a film thickness of 0.
The coating was applied so as to have a thickness of 8 μm to obtain an antistatic layer B-30.

<< Undercoating Coating Solution a-30 >> The same as the undercoating coating solution a-1 in Example 1.

<Undercoating coating solution a-31> The same as the undercoating coating solution a-2 in Example 1.

<< Antistatic Coating Composition b-30 >> Copolymerized latex liquid of butyl acrylate 40% by weight, butylene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 270 g Compound (C-6) 0.6 g Hexamethylene-1,6-bisethyleneurea 0.8 g π-electron conductive polymer component (see Tables 9, 10 and 11) 100
Weight water to reach mg / m ² (Ca ²⁺ concentration 2200ppm, 1100ppm, 66
0 ppm, 200 ppm, and 10 ppm were arbitrarily used) to finish the composition to 1 liter, adjust the pH to 7.0, and disperse with a stirrer and a sand mill to prepare.

The following magnetic recording layer coating liquid c-1 was applied to the B-21 and B-30 surfaces of the TAC and polyethylene-2,6-naphthalate films which had been subjected to the undercoating and antistatic treatment, respectively, on the side opposite to the photosensitive layer. The coating was applied so that the dry film thickness was 1.0 μm, and the magnetic recording layers were C-22 and C-31, respectively.

<Magnetic Recording Layer Coating Liquid c-1> 10 parts by weight of carnauba wax was dissolved by heating in 150 parts by weight of toluene, cooled, and then mixed with 75 parts by weight of cyclohexanone and 150 parts by weight of methyl ethyl ketone, and then Asahi Kasei Corporation. Made by Nitrocellulose BTH-1 / 2 100 parts by weight (solid content 70% by weight) and Co deposited γ-Fe ₂ O ₃ (major axis 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 oersted) 5 Part by weight was added, and the mixture was mixed for 1 hour with a dissolver, and then dispersed with a sand mill to obtain a dispersion liquid.

Silver halide color photographic light-sensitive materials were prepared by sequentially applying the following multilayer color photographic constituent layers to the A-20 surface of the processed TAC film and the A-31 surface of the polyethylene-2,6-naphthalate film. .

<Coating of Color Photographic Constituent Layer> As it is on the A-20 side of the above processed TAC film, and 25 on the A-3 1 side of polyethylene-2,6-naphthalate film.
After a corona discharge of W / (m ² · min), a multilayer color photographic constituent layer was coated.

The coating amount in the photographic constituent layers shown below is the amount expressed in g / m ² unit in terms of metallic silver for silver halide and colloidal silver, and g / m for couplers and additives. Amounts expressed in m ² units and, for sensitizing dyes, are expressed in moles per mole of silver halide in the same layer.

<< 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 << 3rd 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 Sensitized dye (SD-1) 1.0 × 10 -4 sensitizing dye (SD-2) 1.0 × 10 -4 sensitizing dye (SD-3) 1.2 × 10 -5 cyan coupler (C-2) 0.14 color Cyan coupler (CC-1) 0.016 High boiling solvent (OIL-1) 0.16 Gelatin 0.7
9 << Sixth Layer: Intermediate Layer >> Compound (SC-1)
0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 << Seventh layer: low sensitivity green sensitive layer >> Silver iodobromide emulsion 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 << Eighth layer: Intermediate layer Gelatin 0.41 <Ninth 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 compound (Di-2) 0.025 DIR compound (Di-3) 0.002 High boiling point solvent (OIL-4) 0.12 Zera Down 0.5
0 <10th layer: high-sensitivity green-sensitive layer> Silver 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 << Eleventh 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 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 increase 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 solvent (OIL-2) 0.42 Gelatin 1.40 << 13th layer: High sensitivity blue sensitivity "Iodobromide emulsion C 0.15 sensitizing dye (SD-9)
8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 << 14th layer: 1st protective layer >> Iodobromide Silver 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 << 15 layers: second protective layer >> Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aids Su-1, Suspension 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 emulsion used in the above sample is 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.

[0264]

[Table 8]

The samples were simultaneously coated with the multi-slide hopper type coater, the first to the eighth layers at the first time, and the ninth to the fifteenth layers on the second time at the same time.
The specific photographic speed was ISO420. The structure of each compound used for the preparation of the sample is shown below.

[0266]

[Chemical 29]

[0267]

Embedded image

[0268]

[Chemical 31]

[0269]

Embedded image

[0270]

[Chemical 33]

[0271]

Embedded image

[0272]

Embedded image

[0273]

Embedded image

[0274]

Embedded image

<Development Processing> The development processing of the above color photographic film sample was performed under the following formulation and conditions.

<< 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 ° C 4. Settling 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ° C or less The composition of the treatment liquid used in each step is shown below.

<< Color Developer Formulation >> 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter (pH = 10.1) << Bleaching liquid formulation >> Ethylenediaminetetraacetic acid iron (III) Ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter and pH was adjusted with ammonia water.
Adjust to 6.0.

<< Fixing Solution Formulation >> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH 6.0 is adjusted using acetic acid.

<< Stabilizer Formulation >> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

<Evaluation Method> (1) Ash adhesion test: The same ash adhesion test as in Example 2 was performed.

(2) Peel static test: A sample was cut into a size of 35 mm width and 1 m length in a dark room, the humidity of the film was adjusted to a dark room environment of 23 ° C. and 80% RH, and the film was wound on a 40 mm core. The end of the tape with tape, the photosensitive layer wrapped inside, the end with tape, the wrapped film enclosed in a sealed can,
After heating in an oven at 50 ° C for 24 hours, opening and peeling in a dark room at 23 ° C and 20% RH, the film was immediately developed, and the degree of color development due to yellow static electricity in the blue sensitive layer was examined. The degree of color development was ranked as follows.

No color formation Rank A A slight amount of color appears to be present in a very small part. B There are 1 to 2 slightly smaller coloring points in the entire length C Coloring points are slightly scattered over the entire length D Coloring points are scattered over the entire length E Coloring is considerably seen F Full surface There is some color development <Evaluation and results>

[0283]

[Table 9]

[0284]

[Table 10]

[0285]

[Table 11]

The evaluation results are shown in Tables 9, 10 and 11. As can be seen from this table, it was found that the antistatic property was improved by lowering the calcium ion concentration of the antistatic coating composition. Good results were obtained especially at 500 ppm or less. Although these antistatic coating compositions were repeatedly adjusted, there was no change in performance and they exhibited stable conductivity. There was no difference between the plastic films (support).

[0287]

EFFECTS OF THE INVENTION The harmful effects of charging of plastic films and silver halide photographic light-sensitive materials are eliminated, and stable products can be produced.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chiaki Otani Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (15)

[Claims] 1. An antistatic coating composition, wherein the calcium ion concentration of an aqueous dispersion or an aqueous solution containing a π-electron conductive polymer and an acceptor dopant is 500 ppm or less. 2. The antistatic coating composition according to claim 1, wherein the aqueous dispersion or the aqueous solution containing the π-electron conductive polymer and the acceptor dopant has a calcium ion concentration of 100 ppm or less. 3. The antistatic coating composition according to claim 1, wherein the calcium ion concentration of the aqueous dispersion or aqueous solution containing the π-electron conductive polymer and the acceptor dopant is 20 ppm or less. 4. The antistatic coating composition according to any one of claims 1 to 3, wherein the aqueous dispersion or aqueous solution contains gelatin as a binder. 5. 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. Naphthenes and their derivatives, thiophene and pyrrole copolymers and their derivatives, polythienylene vinylene and its derivatives, polyselenophene and its derivatives, and their π
The antistatic coating composition according to any one of claims 1 to 4, wherein the electronically conductive polymer is at least one of branched polymers linked to another chain polymer. Stuff. 6. A calcium ion concentration of 500 p, containing a π-electron-type conductive polymer and an acceptor dopant.
A plastic film having at least one layer coated with an antistatic coating composition consisting of an aqueous dispersion or an aqueous solution of pm or less. 7. A calcium ion concentration of 100 p containing a π-electron conductive polymer and an acceptor dopant.
7. The plastic film according to claim 6, which has at least one layer coated with an antistatic coating composition consisting of an aqueous dispersion or an aqueous solution of pm or less. 8. A calcium ion concentration of 20 pp, containing a π-electron conductive polymer and an acceptor dopant.
7. The plastic film according to claim 6, which has at least one layer coated with an antistatic coating composition comprising an aqueous dispersion or an aqueous solution having a size of m or less. 9. The plastic film according to claim 6, wherein the aqueous dispersion or aqueous solution contains gelatin as a binder. 10. 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. Naphthenes and their derivatives, thiophene and pyrrole copolymers and their derivatives, polythienylene vinylene and its derivatives, polyselenophene and its derivatives, and their π
The plastic film according to any one of claims 6 to 9, wherein the electronically conductive polymer is at least one of branched polymers linked to another chain polymer. 11. A π-electron conductive polymer and an acceptor dopant are contained, and the calcium ion concentration is 50.
Halogen characterized by having at least one silver halide emulsion layer on a plastic film support having at least one layer coated with an antistatic coating composition consisting of an aqueous dispersion or an aqueous solution of 0 ppm or less. Silver halide photographic light-sensitive material. 12. A calcium ion concentration of 10 containing a π-electron conductive polymer and an acceptor dopant.
A plastic film support having at least one layer coated with an antistatic coating composition comprising an aqueous dispersion or an aqueous solution of 0 ppm or less, and having at least one silver halide emulsion layer. Item 12. A silver halide photographic light-sensitive material according to item 11. 13. A π-electron conductive polymer and an acceptor dopant are contained, and the calcium ion concentration is 20.
A plastic film support having at least one layer coated with an antistatic coating composition comprising an aqueous dispersion or an aqueous solution having a ppm or less, and having at least one silver halide emulsion layer. Item 12. A silver halide photographic light-sensitive material according to item 11. 14. The silver halide photographic light-sensitive material according to any one of claims 11 to 13, wherein the aqueous dispersion or aqueous solution contains gelatin as a binder. 15. 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. Naphthenes and their derivatives, thiophene and pyrrole copolymers and their derivatives, polythienylene vinylene and its derivatives, polyselenophene and its derivatives, and their π
15. The silver halide photographic light-sensitive material according to claim 11, wherein the electronically conductive polymer is at least one of branched polymers linked to another chain polymer. material.