JPH08211555A - Silver halide photographic sensitive material with antistatic layer - Google Patents

Abstract

PURPOSE: To provide a sensitive material having semipermanent antistatic performance, not generating unfavorable static marks, etc., owing to electrification, having such antistatic performance as not to stick dust and preventing the deterioration of the antistatic performance with the lapse of time by forming an antistatic layer contg. an electrically conductive polymer having a π electron system, aq. copolyester and a crosslinking agent on one side of a plastic film. CONSTITUTION: An electrically conductive polymer having a πelectron system is mixed with or dispersed in aq. copolyester, a crosslinking agent is further added and one side of a plastic film is coated with the resultant antistatic compsn. to obtain a substrate. Adhesiveness especially in an alkaline processing soln. and stability of the formed antistatic layer itself or stability of the appliability of a silver halide emulsion, etc., applied on the antistatic layer are attained. Aq. copolyester contg. an alkali metallic sulfonate and arom. dicarboxylic acid may be used and polyethylene glycol may further be added as a modifying component to the aq. copolyester. Suitability to coating with an upper layer can further be improved.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having an antistatic ability. Specifically, it relates to a silver halide photographic light-sensitive material having a permanent antistatic property.

[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 or a photographic film) is apt to be damaged by electrification during the manufacturing process or during transportation in a camera, The accumulated static electricity generated due to contact friction with the surface of the same kind or different kind of material, peeling, etc. discharges and causes troublesome defects which 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 takes a photograph and develops the defect to find it, 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 has been proposed which has an antistatic property permanently by an electronic conductive substance such as metal oxide particles and π-electron conductive polymer.

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, It does not delay drying, does not contaminate the transport roller, does not reduce the adhesive strength between the constituent layers of the photographic light-sensitive material, can be manufactured stably during the manufacturing process, and has no change in performance due to aging. 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]

When the π-electron conductive polymer is coated and processed as an aqueous antistatic composition, the antistatic layer has the π-electron conductive polymer present as particles in the aqueous dispersion. In many cases, there is a problem in film forming performance, the layer containing only the polymer is fragile, or physical or mechanical performance to be provided as a silver halide light-sensitive material, such as a support, an emulsion layer or a back layer. There were many obstacles to its practical use, such as weak adhesion to the like, easy scratches, etc. The silver halide photographic light-sensitive material has a water-based development treatment after exposure, etc., and when the film-forming performance is not very good, the film may loosen during the treatment and the adhesion may deteriorate.

In order to eliminate such defects, European Patent No. 0602713A1 in which a π-electron-type conductive polymer is mixed with a hydrophilic polymer latex to improve the adhesion has been proposed as the following method of antistatic coating. There is. However, as a result of studying this by the present inventor, although the antistatic performance or some kind of adhesive performance is improved, the adhesiveness with an alkaline treatment liquid, the coatability of the antistatic composition itself, the coating of the coating thereon. Property, for example, when coating another layer such as a silver halide emulsion layer or a protective layer on the antistatic layer,
It was found that important defects of the silver halide photographic light-sensitive material such as loss of coating uniformity are caused. Further, deterioration of the antistatic performance and coating property of the antistatic composition after application of the composition after preparation of the antistatic composition were observed. In the coating property, the coating property of the antistatic composition itself may be deteriorated on the surface of the antistatic layer as described above, but when another layer is coated on the antistatic layer, the local coating property may be deteriorated. I found out.

A first object of the present invention is to have semi-permanent antistatic performance, to prevent generation of inconvenient static marks due to charging, and to have excellent charging performance in which dust does not adhere.
Another object of the present invention is to provide a silver halide photographic light-sensitive material having an antistatic layer that does not deteriorate in charging performance with time. The second object is to provide a silver halide photographic light-sensitive material having an antistatic layer having strong adhesion between the antistatic layer and a support or another coating layer. The third object is to provide a silver halide photographic light-sensitive material having an antistatic layer having excellent coating properties. A fourth object is to provide a silver halide photographic light-sensitive material having an antistatic layer having stable performance with an antistatic composition which is resistant to deterioration even after storage for a long time.

[0008]

Means for Solving the Problems: 1) An antistatic composition prepared by mixing or dispersing a π-electron conductive polymer in an aqueous copolyester and adding a crosslinking agent to the system is applied to at least one surface of a plastic film. By providing the support as a support, the above problems, particularly the adhesiveness in an alkaline processing liquid, and the stability of the coating property of the antistatic layer itself or of the silver halide emulsion coated thereon can be achieved. Obtained. 2)
By using an aqueous copolyester containing an alkali metal salt sulfonate aromatic dicarboxylic acid, and by further adding polyethylene glycol to the aqueous copolyester as a modifying component, the coatability of the upper layer can be further enhanced, and the coatability can be improved. Was achieved. 3) Furthermore, a silver halide photographic light-sensitive material having strong adhesiveness could be obtained. 4) In the system of 1) or 2) above, the general formula (I) and / or
Further, by adding the antiseptic of (II), the problem of deterioration of the coating property due to stagnation of the antistatic composition over time was solved, and good coating property could be achieved.

[0009]

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[0010]

[Chemical 4]

The present invention will be described in detail below.

The π-electron conductive polymer of the present invention is a conjugation having a conjugated structure in which a double bond or a triple bond connecting a carbon atom and a carbon atom or a hetero atom is alternately long and continuous with a single bond as a molecular skeleton. It is a polymer. As these conjugated polymers, 1) aliphatic conjugated systems: polymers in which carbon-carbon conjugated systems such as polyacetylene are alternately and continuously long, 2) aromatic conjugated systems: aromatic hydrocarbons such as poly (paraphenylene) A polymer in which conjugation has been developed in which a long bond is formed, 3) a heterocyclic conjugated system: a polymer in which a conjugated system is developed by binding a heterocyclic compound such as polypyrrole or polythiophene, 4) a hetero atom-containing conjugated system: a fat such as polyaniline Polymers in which a conjugated system of group or aromatic is bound by a hetero atom, 5) Mixed conjugated system: Conjugated polymer having a structure in which constituent units of the above conjugated system such as poly (phenylene vinylene) are alternately bonded, 6) Multiple Chain-type conjugated system: A conjugated system having multiple conjugated chains in the molecule, a polymer having a structure similar to an aromatic conjugated system, 7) Metal phthalocyanine system: Metal phthalocyanine Polymers or polymers in which these molecules are bound by heteroatoms or conjugated systems, 8) Conductive composites: polymers in which the above conjugated polymer chains are graft-copolymerized with a saturated polymer, and the above conjugated polymers are polymerized in a saturated polymer. Examples thereof include the composites obtained by doing so, and the conjugated polymer can be applied to the present invention as a π-electron 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.

Further, 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.

[0016]

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[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

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[0020]

[Chemical 9]

[0021] Here 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 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,
It represents an alkylsulfo group or a salt thereof, an alkylcarboxyl group or a salt thereof, or an alkylsulfoamide group, and a hydrogen atom is particularly preferable. Further, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R _X may be the same or different. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , R ₉ and R ₁₀ , R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ ,
R ₁₅ and R ₁₆ and R ₁₇ and R ₁₈ may be bonded to each other to form a ring.

These R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ 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 At least one group selected from 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.

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 AS
As shown by P (V), one of them is the other chain polymer main chain P ₁ and the π electron system conductive polymer A.
It may be bonded to a divalent linking group L that connects to.

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 (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, di-acetic acid, etc.) 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.

[0028]

[Chemical 10]

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 composition of the present invention is preferably 0.5 to 50% by weight in the composition in order to enhance the conductivity when applied as an antistatic layer, Particularly, 1 to 20% by weight is preferable.

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 conductive polymer of the present invention as a repeating unit in the side chain,
Among the main chains (P ₁ + P ₂ ) of the composite polymer, the molar ratio P ₂ / (P ₁ + P ₂ ) of the main chain polymer (P ₂ ) having no π-electron conductive polymer is arbitrary. Good, but 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 of 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, No. 2-252726, No. 0593111A1, No. 0602713A1, J, Chem.Soc.Chem.Commu.
n., 1983, p. 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, the monomer and the conductive salt are dissolved or dispersed in water or an organic solvent to immerse the positive and negative electrodes, and the temperature is -30 to 90 ° C, preferably -10 to 90 ° C. 5
At constant temperature method, constant voltage method, constant potential method or constant current method.

As 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.

As the conductive salt used in the electrolytic oxidation polymerization method, 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 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.

The 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 composition of the present invention. When the π-electron conductive polymer of the present invention is a powder, a mesh is prepared using a ball mill or the like so that it can be dispersed in a fine particle form, and the average particle size is pulverized to 0.05 to 1 μm, preferably 0.1 to 0.5 μm, and then the interface It is preferable to disperse the fine particles by adding a dispersant such as an activator and a water-soluble polymer to water. 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 already contained and the dispersant is not necessary in principle, but it may be added if necessary.

The π-electron-type conductive polymer used in the present invention is usually preferably used in a state where it is doped with a dopant. As the dopant, an acceptor dopant is preferably used, and a halogen molecule (eg, Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF), Lewis acid (eg, PF ₅ , AsF ₅ , SbF ₅ , BF) is used. ₃ , BCl ₃ , BBr ₃ , S
O ₃ ), protic acid (eg HF, HCl, HNO ₃ , H ₂ SO ₄ , HC
lO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, various organic acids, amino acids, etc., transition metal compounds (eg FeCl ₃ , FeOCl, TiCl)
₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoF ₅ , MoCl ₅ ,
_{WF 6, WCl 6, LnCl 3} (Ln = La, Ce, Pr, 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 C
^{_{O 2 -, CH 3 SO 3}} -, CH 3 C 6 H 5 SO 3 -), a polymer electrolyte anions (e.g. polyvinyl sulfate, polystyrene sulfonic acid,
Poly (p-vinylbenzyl sulfonic acid), polyacrylic acid,
Polyethylene sulfonic acid, polyvinyl sulfonic acid, polyphosphoric acid, polyaspartic acid), etc., as well as O ₂ and XeO
^{_{F 4, (NO 2 +)}} (SbF 6), (NO 2 +) (SbCL 6 -), (NO 2 +) (BF 4 -), FS
Examples thereof include O ₂ OOSO ₂ F, AgClO ₄ , H ₂ IrCl ₆ , La (NO ₃ ) ₃ .6H ₂ O and the like, but are not limited thereto. I ₂ ,
_{Br 2, HCl, H 2 SO} 4, AsF 5, SbF 5, KBF 4, LiBF 4, (C 2 H 5) 4 N
BF ₄ , FeCl ₃ , LiClO ₄ , CF ₃ SO ₃ Li, CF ₃ SO ₃ Na, CF ₃ SO ₃ H, L
iBr, p-toluenesulfonic acid, polystyrenesulfonic acid and the like are preferably used. The number average molecular weight of polystyrene sulfonic acid useful in the present invention is preferably 1,000 to 1,000,000 in the present invention, from the doping effect of the dopant 3,
Particularly preferred is 0000 to 100,000.

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 performed with a substance in which a dopant is present in the polymerization field of the π-electron type conductive polymer. Further, a dopant may be added at the time of preparing the antistatic 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. Needless to say, it may be included in the doping range of the present invention because it may function as a dopant by doping the π-electron-type conductive polymer.

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.

[0052]

[Chemical 11]

[0053]

[Chemical 12]

[0054]

[Chemical 13]

[0055]

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[0056]

[Chemical 15]

[0057]

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[0058]

[Chemical 17]

[0059]

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[0060]

[Chemical 19]

[0061]

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[0062]

[Chemical 21]

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

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

[0065] 1-2) taking poly (3,4 Synthesis of dimethoxy-pyrrole) [ASP (I) -6] 3,4-dimethoxy-pyrrole 12g, a _{(C 4 H 9) 4 NBF} 4 4g and acetonitrile 200 ml, To this solution at room temperature with stirring under nitrogen atmosphere, 70 g of Fe dissolved in 30 ml of distilled water was added.
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 11 and 12 above.

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

2-2) Synthesis of poly-3,4-diethoxythiophene [ASP (I) -17] 30 g of polystyrenesulfonic acid (number average molecular weight 3,700) was added.
Dissolved in 1.5 liters of water, under nitrogen stream, into it 72 mmol K ₂ S ₂ O ₈ , 0.375 mmol Fe ₂ (SO ₄ ) ₃ , 210 mmol
3,4-Diethoxythiophene was added, and the mixture was reacted at 20 ° C. for 24 hours with stirring. To this was further added 750 ml of water, and strongly acidic and weakly basic ion exchange resins (Amberlite (registered trademark) IR120 and IRA400, respectively, were added to the mixture, and the mixture was mixed at room temperature for 8 hours for desalting. After that, the ion exchange resin was filtered off to obtain a poly-3,4-diethoxythiophene dispersion liquid.
This had an average degree of polymerization of 40 by MR.

2-3) Method for synthesizing poly-3,4-diethoxythiophene 2 1.5 mol of iron trichloride was added to 1 liter of nitrobenzene and heated to 100 ° C. under a nitrogen stream to give 2-chloro-3,4-diethoxythiophene 0 .
5 mol was added dropwise over 1 hour. After dropping, the mixture was stirred at 60 ° C. for 6 hours, the nitrobenzene solution was concentrated, 500 ml of ethyl acetate was added to the solution, and the mixture was extracted by heating and purified by a Sephadec column to obtain 70 g of poly-3,4-dimethoxythiophene.
Polystyrene sulfonic acid (number average molecular weight 3,00
0) Poly-3,4-dimethoxythiophene was dispersed in 12.6 g of 630 ml aqueous solution and stirred at room temperature for 8 hours to obtain a dispersion.

2-4) The above 2-1), 2-2) and 2-
Similarly, according to the synthetic method of 3), ASP (I) -11, 12, 13, 1
4, 15 and 16 were obtained. The average degree of polymerization is described in Chemical formulas 12 and 13 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 11 and 15 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 15 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. After further stirring for 2 hours, 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 or change in particle size. 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, using ITO plate (surface resistance value 10 / □) for working electrode, Pt plate for counter electrode, Li / Li ⁺ for reference electrode, electrochemical at constant voltage of 2.5V for 30 minutes Polymerization resulted in the formation of a film of poly (5-dodecylbenzo [c] thiophene) 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 (I) -19, 21 and 22 were similarly obtained by the synthetic method of 3-2). The average degree of polymerization and the dopant are described in Chemical formula 14 above.

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

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

4-3) ASP (II) -2, 3, 4, 5, 6, 7, 8, 9, 1 using the method of 4-1 and 4-2).
0 and 11 were synthesized. The average degree of polymerization and the dopant of each of these are described in Chemical formulas 16 and 17 above.

5-1) Poly (paraphenylene vinylene)
[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 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 this by elemental analysis and NMR, it was poly (paraphenylene vinylene) and the average degree of polymerization was 200. Doping was performed by immersing this film in a 5 wt% polystyrene sulfonic acid solution for 3 hours.

5-2) Synthesis of poly (3,6-dimethoxyparaphenylenevinylene) [ASP (IV) -2] 1,4 dichloromethyl-3,6-dimethoxybenzene 0.1 mol 2
It was dissolved in 00 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) was added. ) Is added to carry out a polymerization reaction, and after 3 hours, the reaction is continued to be neutralized, and 100 ml of methanol is further added to carry out a reaction, followed by precipitation in a large amount of water to wash, drying and dissolving in tetrahydrofuran, and then a stainless steel plate. It was cast on the above, dried, peeled from the plate, and then heated in an oven at 250 ° C. for 30 minutes to obtain a transparent film.
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 are similarly prepared by any one of the above 5-1) and 5-2) two methods.
Was synthesized. The average degree of polymerization and the dopant are described in Chemical formula 18 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 monomer of P ₁ ,
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 give 2-4-aminophenylaminoethyl methacrylate (C) 200 g.
I got

(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).

(D) 3 g, aniline 4.5 g, 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)-
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 19, 20 and 21 above. Indicated.

Although there is an example in which gelatin is used as a binder in an antistatic composition containing a π-electron conductive polymer, the binder is included in the antistatic composition containing a π-electron conductive polymer of the present invention. Is characterized by using an aqueous copolyester capable of imparting more excellent properties.

In the antistatic composition containing the π-electron conductive polymer of the present invention, the aqueous copolyester is used in the state of an aqueous dispersion or aqueous solution, and the antistatic composition can be easily prepared by a usual method. Can be done. 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.

The aqueous copolyester of the present invention is a modified polyester having properties such that it can be dispersed in water or can be formed into an aqueous solution, and phthalic acid or naphthalenedicarboxylic acid and ethylene glycol are used as the copolyester. The main constitutional unit of the above, in addition to these, a hydrophilic group in the constitutional unit to the extent that it can be water-soluble or aqueous dispersion,
It is a copolyester having some other modified constitutional units. The aqueous copolymer is described below.

The aqueous copolyester of the present invention preferably has polyethylene terephthalate or polyethylene naphthalate as the main constituent component of the copolyester as described above. 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 units are 30 to 80 mol% of all polyester constitutional units, preferably 40 to 65%.
It means that there is 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 diesters of these aromatic dicarboxylic acids with C ₁ -C ₄ alcohols or C ₂ -C ₁₀ glycols. ;
Aliphatic dicarboxylic acids such as adipic acid and sebacic acid, or diesters of these aliphatic dicarboxylic acids with C ₁ -C ₄ alcohols or dihalf esters of C ₂ -C ₁₀ glycols; polyethylene oxide dicarboxylic acids, polypropylene oxide dicarboxylic acids An acid component such as a polyether dicarboxylic acid such as an acid or a diester with a C _{1 to} C ₈ alcohol or a dihalf ester with a C _{2 to} C ₁₀ glycol, ethylene glycol, propylene glycol,
It is composed of glycols such as butanediol, neopentyl glycol, p-xylidene glycol, 1,4-cyclohexanedimethanol, etc .; ester or polyester components with glycol components such as glycols of diethylene glycol and triethylene glycol.

As the metal sulfoaromatic dicarboxylic acid as a modifying component which imparts water solubility or water dispersibility to the aqueous copolyester of the present invention, isophthalic acid containing a metal salt sulfonate group is preferable, and the metal ion is sodium, potassium or lithium. , An alkali metal such as cesium, preferably sodium, specifically 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid or These dimethyl esters and ethylene glycol dihalf esters can be mentioned, and also glycol half esters represented by the following chemical formula 22 can be mentioned, but preferably 5-sodium sulfoisophthalic acid or its dimethyl ester or ethylene glycol dihalf ester. It is. It is preferable that the metal salt is contained in an amount of 5 to 35 mol% based on all ester bonds of the copolyester of an aromatic dicarboxylic acid having a sulfonate group. It is preferably 7 to 30 mol%. It is particularly preferably 10 to 25 mol%.

[0095]

[Chemical formula 22]

As the hydrophilic component other than the sulfonate group of the aqueous copolyester of the present invention, polyethylene glycols are useful for further improving the coating performance. As the polyalkylene glycols, polyethylene glycol is preferable, and the average degree of polymerization is not particularly limited, but preferably 10 to 10,000, more preferably 20 to 10,000.
8,000, particularly preferably 30 to 3,000. The content of the polyalkylene glycol aqueous copolyester is preferably 3 to 20% by weight based on the total weight of the polyester, and the content is preferably 4 to
15% by volume. The water-based copolyester of the present invention containing this polyethylene glycol as a modifying component is particularly useful because the coating property is further improved.

Other examples of the aliphatic dicarboxylic acid as a modified modifying component include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like, with adipic acid, suberic acid and azelaic acid being preferred, and adipic acid being particularly preferred. Acids are preferably used. The amount of the aliphatic dicarboxylic acid polyester is preferably 3 to 10% by weight, preferably 4 to 8% by weight, based on the total weight of the polyester. When the polyalkylene glycol and the aliphatic dicarboxylic acid are used together,
A total of 3 to 20% by weight is preferable, and 4 to 15% by weight is particularly preferable.

The following compounds can be used as a modifying component in the aqueous copolyester of the present invention. Polyetherdicarboxylic acids such as polyethyleneoxydicarboxylic acid, polypropyleneoxydicarboxylic acid, poly (ethylene / propylene) oxydicarboxylic acid, polytetramethyleneoxydicarboxylic acid and copolymers thereof are preferable, but in view of the polymerization reactivity of the copolyester. In particular, it is more preferable to use a polyethyleneoxydicarboxylic acid ester represented by the following formula.

R ⁹ OOCCH _2- (OCH ₂ CH ₂ ) _p -OCH ₂ COOR ¹⁰ wherein R ⁹ and R ¹⁰ are hydrogen or an alkyl group having 1 to 8 carbon atoms, and p is a positive integer of 1 to 100. is there. The modification ratio of the polyether dicarboxylic acid component is 2 to 30% by weight, preferably 5 to 15% by weight, and particularly preferably 7 to 12% by weight based on the total weight of polyester.

Intrinsic Viscosity of Aqueous Copolyester Resins Useful in the Present Invention (Measured with Uvelode Viscometer at 25 ° C. Using a Mixture of Phenol: o-Chlorophenol 60:40)
Is preferably 0.30 to 0.85, and particularly preferably 0.40 to 0.60 from the viewpoint of film forming property.

The aqueous copolyester resin can be synthesized according to a conventionally known method for producing polyester.
For example, in the esterification reaction, either direct esterification of an acid component with a glycol component or 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 ethylene glycol diester (more specifically, ethylene glycol dihalf ester). At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for the esterification and a polymerization reaction catalyst such as antimony trioxide in the polymerization reaction. Regarding the polyester constituents and the synthetic method described above, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pages 103 to 136, or "Synthetic Polymer V" (Asakura Shoten) , 1971) pp. 187-286.

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

Examples of the catalyst used for the transesterification include acetates, fatty acid salts, carbonates of metals such as manganese, calcium, zinc and cobalt. Of 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.

To obtain the copolyester, the acid component and the glycol component may be transesterified, and then the above-mentioned modified 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 the copolyester (after transesterification) include antimony trioxide, zinc oxide, manganese dioxide, titanium dioxide and the like.
Of these, antimony trioxide is preferable.

A synthetic example of the aqueous copolyester is shown below.

(Synthesis of CP-1) 38.74 parts by weight of terephthalic acid dimethyl ester, 3 parts of isophthalic acid dimethyl ester
1.95 parts by weight, sodium-5-sulfoisophthalic acid dimethyl ester 10.34 parts by weight, ethylene glycol 54.48 parts by weight are mixed, calcium acetate monohydrate 0.073 parts by weight and manganese acetate 0.024 parts by weight are added, and the mixture is mixed under nitrogen flow to 1
After carrying out the transesterification reaction while distilling off methanol at 70 to 220 ° C, 0.05 parts by weight of trimethyl phosphate, 0.04 parts by weight of antimony trioxide as a polymerization catalyst and 17.17 parts by weight of 1,4-cyclohexyldicarboxylic acid were added to 220 to 220 ° C. The esterification was carried out at a reaction temperature of 235 ° C. by distilling off almost the theoretical amount of water.
After that, the pressure inside the reaction system was further reduced and the temperature was raised to 280 ° C,
Polycondensation was carried out at 0.2 mmHg for 2 hours. The obtained copolyester resin CP-1 had an intrinsic viscosity (as described above) of 0.45. The resulting aqueous copolyester was used for an antistatic composition and stirred in hot water at 95 ° C. for 3 hours to give a 15% aqueous solution.

(Synthesis of CP-2) 0.1 part by weight of calcium acetate monohydrate was added to 83 parts by weight of terephthalic acid, 41.5 parts by weight of isophthalic acid and 77 parts by weight of ethylene glycol, and esterification reaction was carried out by a conventional method. . 5-in the product obtained
55 parts by weight of sodium sulfodi (β-hydroxyethyl) isophthalic acid in ethylene glycol solution (concentration 35% by weight)
Polyethylene glycol (average degree of polymerization of 2,000
0) 13 parts by weight, antimony trioxide 0.05 parts by weight, tetramethylammonium hydroxide 0.15 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight were added. Next, gradually raise the temperature to 255 ° C, reduce the pressure, and then 1.5 at 280 ° C and 0.2 mmHg.
Polymerization was carried out for a period of time and cooled to obtain a copolyester resin CP-2 having an intrinsic viscosity of 0.52. In order to use the obtained aqueous copolyester in an antistatic composition, it was stirred in hot water at 95 ° C. for 3 hours to give a 15% by weight aqueous solution.

(Synthesis of CP-3) 0.1 part by weight of zinc acetate dihydrate was added to 95 parts by weight of terephthalic acid, 20 parts by weight of isophthalic acid and 90 parts by weight of ethylene glycol, and esterification reaction was carried out by a conventional method. The obtained product was concentrated with 45 parts by weight of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid and 8 parts by weight of adipic acid in an ethylene glycol solution.
In addition to 35% by weight, 0.07 part by weight of antimony trioxide and 0.13 part by weight of trimethyl phosphate were added. Then, the temperature was gradually raised to 255 ° C under a nitrogen stream, the pressure was reduced, ethylene glycol was allowed to flow out, 285 ° C was polymerized at 0.7 mmHg, and a copolyester resin CP-3 similarly having an intrinsic viscosity of 0.50 was obtained.
I got 20% by weight of the obtained aqueous copolyester was stirred in hot water at 95 ° C for 3.5 hours for use in an antistatic composition.
Of water dispersion.

Both of the copolyesters may contain phosphoric acid, phosphorous acid and their esters and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.) at the polymerization stage, or the polymer after polymerization may be contained. Inorganic particles and the like may be blended. Further, a pigment, an ultraviolet absorber, an antioxidant, a matting agent, a slip agent, a stabilizer, a surfactant, a dispersant, an anti-tacking agent, a softening agent, etc. are appropriately added at the polymerization stage or at any stage after the polymerization. It doesn't matter. 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 commercially available products can be used.

The silver halide photographic light-sensitive material of the present invention has an antistatic layer containing a π-electron conductive polymer, an aqueous copolyester and a crosslinking agent. A hydroxyl group and a carboxy group are present at the ends of the aqueous copolyester molecule, and a crosslinking agent capable of reacting with these is used. Further, a crosslinking agent which does not adversely affect the silver halide emulsion layer must be selected. As such a cross-linking agent, a so-called hardener which is usually used in silver halide photographic light-sensitive materials is preferable. The reaction speed of these cross-linking agents is very mild, and when they are reacted with gelatin binders such as ordinary silver halide emulsions, the temperature is at most about 40 ° C, and it takes several hours to stabilize for several weeks. There are some, but a high temperature is required to accelerate the reaction. When the temperature is raised, the reaction time can be shortened. In the present invention, in order for the crosslinking agent to react with these reactive groups of the aqueous copolyester, it is preferable to apply heat of at least 80 ° C. or higher.

The antistatic layer of the present invention can be formed on a plastic film by coating the film with an antistatic coating composition and then drying it. Is different as follows.

1) A method of subjecting a biaxially stretched (including commercially available) plastic film to an undercoating treatment (including an antistatic layer treatment, hereinafter sometimes referred to as an undercoating treatment) in a separate step. Method of performing in-line subbing treatment before uniaxial stretching, longitudinal stretching and subsequent transverse stretching, and heat treatment in heat setting 3) After uniaxial stretching of the film manufacturing process, inline subbing treatment before biaxial stretching, transverse stretching, Also, there is a method of heat treatment utilizing heat during heat setting, and the crosslinking treatment can be carried out by any one of the above-mentioned subbing heat treatments. The above production condition 1) allows heat treatment at about 160 to 200 ° C. in the subbing heat treatment step, but it is difficult to convey the film web at a temperature higher than that, but if it is within that temperature range, crosslinking will occur. Can be done reliably. The manufacturing condition 2) is not so preferable because the film forming apparatus is complicated in the undercoating treatment before the longitudinal stretching. The above-mentioned production condition 3) is the most preferable method particularly in terms of heating temperature and heating time in the film forming step. In manufacturing condition 3), 230 ~ 2 in heat setting process
This is because a temperature of 60 ° C can be applied.

Conventionally, the crosslinking of polyesters has conventionally been carried out in a non-aqueous manner such as isocyanate, but it has been originally said that crosslinking of aqueous copolyesters is difficult. The present inventor has discovered that the following hardeners used for silver halide photographic light-sensitive materials can be crosslinked under the above-mentioned production conditions.

When the copolyester as the binder of the antistatic composition containing the π-electron conductive polymer of the present invention is crosslinked with the crosslinking agent of the present invention, the adhesiveness, particularly the adhesiveness in an alkaline treatment liquid is improved. To do. When it is not crosslinked, the membrane falls in the alkaline treatment solution so as to dissolve from the support, but such a phenomenon does not appear in the present invention. When gelatin is used as the binder, the adhesiveness is good, but water is likely to be absorbed and the drying tends to be slow.

As the cross-linking agent used in the present invention, those used in silver halide photographic light-sensitive materials such as epoxy type, aldehyde type, active ethylene type, active ester type, aziridine type and N-methylol type are used. Can be done.

The epoxy-based crosslinking agent used in the present invention is
Those having two or more epoxy groups in the molecule and having a molecular weight per functional group of 300 or less are preferable. Further, those having an ether bond or a hydroxy group in the crosslinking agent molecule are particularly preferable. Here, the molecular weight per functional group means a value obtained by dividing the total molecular weight of the crosslinking agent by all the functional groups. Specific examples of the epoxy cross-linking agent are shown below, but the epoxy cross-linking agent is not limited thereto.

[0118]

[Chemical formula 23]

[0119]

[Chemical formula 24]

The aldehyde-based cross-linking agent used in the present invention has two or more aldehyde groups in the molecule, and formaldehyde, glyoxal, glutaraldehyde, succinaldehyde, mucochloric acid and the like are used, but are not limited thereto. It is not something that will be done.

The active ethylene-based crosslinking agent used in the present invention is one in which the active ethylene group has two or more vinyl sulfone groups or acryloyl groups in the molecule, and the molecular weight per functional group is 500 or less. preferable. Specific examples of the active ethylene crosslinking agent are shown below, but the invention is not limited thereto.

[0122]

[Chemical 25]

[0123]

[Chemical formula 26]

The aziridine-based crosslinking agent used in the present invention has two or more aziridine groups, and preferably has a molecular weight of 300 or less per functional group. Specific examples of the aziridine crosslinking agent are shown below, but the invention is not limited thereto.

[0125]

[Chemical 27]

[0126]

[Chemical 28]

Specific examples of the cross-linking agent classified as the active ester cross-linking agent used in the present invention are shown in the following patent documents, for example:
JP-A-49-51945, JP-A-51-59625, Belgium Patent No. 825,72
6, JP-A-60-225148, 51-126125, 52-48311
No. 57, No. 57-44140, No. 57-54427, No. 58-50669,
JP 61-9641, JP 50-38540, 52-93470,
The compounds described in JP-A-56-43353, JP-A-58-113929, and US Pat. No. 3,321,313 can be mentioned. The active ester-based crosslinking agent acts on the free carboxyl group of the polymer to be crosslinked to activate the carboxyl group,
A compound that reacts with a nucleophile. Incidentally, this may be interpreted as a dehydrating agent.

Specific examples of the above active ester crosslinking agent are shown below, but the present invention is not limited thereto.

[0129]

[Chemical 29]

[0130]

Embedded image

[0131]

[Chemical 31]

[0132]

Embedded image

[0133]

[Chemical 33]

The above-mentioned active ester crosslinking agent is disclosed in JP-A-49-5
It can be synthesized by the methods disclosed in 1945 and 51-59625. Also, Belgian Patent No. 825,726, JP-A-60-
225148, 51-126125, 52-48311, 57-44140
No. 57-54427, JP-B-58-50669, JP-A-61-9641
It can also be synthesized according to the synthetic method disclosed in each publication.

Examples of the N-methylol crosslinking agent used in the present invention include the following compounds.

[0136]

Embedded image

Of the above-mentioned crosslinking agents, active ethylene-based crosslinking agents,
Active ester crosslinking agents, epoxy crosslinking agents and aziridine crosslinking agents are preferred.

When the antistatic composition containing the π-electron conductive polymer, the aqueous copolyester and the cross-linking agent of the present invention is aged in the form of an aqueous dispersion or an aqueous solution, microorganisms such as bacteria and fungi are easily proliferated and altered. However, a deterioration phenomenon of coating property is apt to appear, and the deterioration can be suppressed by adding a preservative.

Examples of preservatives include phenol, thymol, trichlorophenol, cresol, o-phenylphenol, p-chlorophenol, chlorophen, 3,4,
5-tribromosalicylanilide, 4-n-hexylresorcin, formaldehyde, paraformaldehyde, glutaraldehyde, methylolchloraldehyde, benzoic acid, p-oxybenzoic acid ester, sorbic acid, 2-mercaptobenzothiazole, 2- (4 -Thiazolyl) -benzimidazole, phenylmercury, phenylmercuric propionate,
Neomycin, kanamycin, etc. are known as general fungicides or antifungal agents. Others: (a) Research Disclosure
sure hereafter abbreviated as RD) No.18751

[0140]

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(B) Compounds described in RD NO.20526, for example:

[0142]

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(C) For example, the following compounds described in JP-A No. 61-107343

[0144]

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(D) For example, the following compounds described in US Pat. No. 3,542,553

[0146]

[Chemical 38]

(E) For example, the following compounds described in JP-A-58-105145

[0148]

[Chemical Formula 39]

(F) For example, the following compounds described in JP-A-60-119547

[0150]

[Chemical 40]

And the like.

Many of these substances are not effective unless they are added in a large amount, they are harmful to the living body, they have a photographic adverse effect, and they are added to the antistatic layer of the present invention. Only a few kinds can be used, because a coating-like defect in a coat-like form is generated, or film adhesion to an adjacent layer such as an emulsion layer is deteriorated. Among these, the compounds represented by the following general formulas (I) and / or (II) are particularly preferable for the present invention because they do not cause tailing defects and do not affect other photographic performances.

[0153]

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In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group, a cyclic alkyl group,
It represents an aryl group, a cyano group, an alkylthio group, an arylthio group, an alkyl sulfoxide group, an alkylsulfonyl group, or a heterocyclic group. However, the alkyl group, cyclic alkyl group, alkenyl group, heterocyclic group, aralkyl group and aryl group may have a substituent. A ring may be wound around R ¹ and R ² . R ³ is a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkylamide group, an arylamide group, an alkylthioamide group, an arylthioamide group, an alkylsulfoamide. Represents a group. In the formula, R ⁴ represents a hydrogen atom, a lower alkyl group, or a hydroxymethyl group, and R ⁵ and R ⁶ represent a hydrogen atom, a lower alkyl group.

Especially preferred in the present invention are the general formulas (I) and / or
Examples of the preservative of (II) are shown below, but the preservatives are not limited thereto.

[0156]

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[0157]

[Chemical 43]

[0158]

[Chemical 44]

[0159]

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[0160]

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[0161]

[Chemical 47]

These compounds are described, for example, in French Patent No. 1,
It can be synthesized by the synthesis method described in the specification of 555,416, or according to this method.

The amount of the compounds of the general formulas (I) and (II) to be used varies depending on the kind of the compound or the dispersion conditions, but it is usually in the range of 0.1 to 100 mg per 1 g,
It may be preferably 0.5 to 50 mg. Upon addition, since it tends to dissolve in water or a hydrophilic solvent such as methanol, ethanol, acetone, or ethylene glycol monomethyl ether, it is preferably dissolved in water before addition. The antistatic composition may be added during the synthesis of the π-electron conductive polymer or during the purification process, or during the preparation of the antistatic composition.

The antistatic composition of the present invention is an aqueous dispersion or an aqueous solution containing a π-electron conductive polymer, an aqueous copolyester and a crosslinking agent, and the aqueous solution may contain an organic solvent. For example, ethylene glycol, propylene glycol, diethylene glycol, formamide,
Dimethyl formamide, dimethyl sulfoxide,
By mixing a solvent having a high boiling point such as polyethylene glycol, glycerin, polyglycerin, etc., it is useful for the pre-stretching undercoating treatment, and when the undercoating layer is stretched together with the film, the undercoating layer can be easily stretched uniformly. Useful for.

Further, a dispersant such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, or a coating aid may be used in the antistatic composition of the present invention. The following compounds are used as dispersants and coating aids.

If necessary, a vinyl polymer may be allowed to coexist in the antistatic composition of the present invention in the form of an aqueous solution such as a latex. Although not particularly required, in the case of coexistence, the coexistence method is to polymerize the vinyl monomer in a latex state in the presence of the aqueous polyester, and in some cases, to bond the aqueous monomer to perform graft polymerization. good. As the polymerization catalyst in this case, a commonly used water-soluble peroxide, redox catalyst, or a compound that decomposes to generate radicals and simultaneously releases nitrogen gas is used. For example _{K 2 S 2 O 8, (} NH 4) 2 S 2 0 8,
H ₂ O _{2 to} Fe ₂ (SO ₄ ) ₃ , disodium-α, α-'azobisisobutylcarboxylate and the like are preferably used.

The weight ratio of aqueous copolyester to vinyl polymer is 99-55 / 1-45, preferably 95-65 / 5-35.
Is.

Monomers that can be used for the vinyl polymer include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate,
Propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 2-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate,
Acrylamide, N-methylacrylamide, N-methoxyacrylamide, N-hexylacrylamide, N-phenylacrylamide, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, glycidyl methacrylate, acrylic acid or its salt, methacrylic acid or Examples thereof include salts thereof, styrene, vinyltoluene, styrenesulfonic acid and salts thereof, but are not limited to these.

If desired, the antistatic composition of the present invention may contain other binders. 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, methyl cellulose, dextrin, polyvinyl pyrrolidone, styrene or alkyl acrylate and sodium styrene sulfonate, acrylic acid and its salts, acrylamide or 2-acrylamide. Examples thereof include copolymers with sodium 2-methylpropanesulfonate and the like, polyacrylamide, polyacrylic acid and sodium, gelatin, and casein. The amount of the binder in the antistatic composition is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the composition. As a raw material of gelatin, there are pigskin, calfskin, ossein and the like, and as a treatment method of gelatin, there are acid treatment and alkali treatment (lime soaking treatment). 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 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.

The water used in the present invention must be distilled.
It is desirable to deionize with an ion exchange resin.

<Antistatic Support> The antistatic plastic film of the present invention (hereinafter abbreviated as “support”) can be obtained by coating the plastic film with the antistatic composition of the present invention.

<Plastic Film> The plastic film according to the present invention includes polyethylene terephthalate, polyethylene naphthalate, modified polyester containing metal sulfoaromatic dicarboxylic acid, polyester containing metal sulfoaromatic dicarboxylic acid and polyethylene terephthalate and / or polyethylene naphthalate. Laminated structure with polyester, polycarbonate, polyamide, polyimide, polyphenyl sulfone, polyphenyl ether, cellulose triacetate, syndiotactic polystyrene, polyethylene, polypropylene, polyethylene laminated film and the like film,
It is not limited to these. Examples of the plastic film useful as the support of the present invention include polyethylene terephthalate, polyethylene naphthalate, modified polyester containing metal sulfoaromatic dicarboxylic acid, and laminate of polyester containing metal sulfoaromatic dicarboxylic acid and polyethylene terephthalate and / or polyethylene naphthalate. Polyester such as structural polyester, syndiotactic polystyrene, polycarbonate, and cellulose triacetate are preferable, and polyester plastic film is particularly preferable from the viewpoint of strong adhesion of the antistatic layer.

Polyethylene terephthalate film is mainly used for printing photographic film or medical photographic film (also called X-ray film), but it is also used for color photographic film. Recently polyethylene-2,6
-Proposals have been made to apply naphthalate, modified polyester films, polycarbonate films, syndiotactic polystyrene, etc. to new photographic films, but these are plastic films as useful and preferable supports in the present invention.

Polyethylene terephthalate film and 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.

The modified polyester film containing a metal sulfoaromatic dicarboxylic acid (herein, the polyester is referred to as a modified polyester in order to distinguish the aqueous copolyester from the polyester) is prepared by the same method as that for polyethylene terephthalate. You can make a film. The laminated polyester film is a film obtained by mainly combining the modified polyester with polyethylene terephthalate and / or polyethylene naphthalate in three or more layers, and using the respective raw materials, a film is formed from an extrusion die for lamination in the same manner as a normal polyethylene phthalate. You can make it. 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 the 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. Here, having many repeating units means that the repeating units are 70 mol% or more, preferably 85 mol% or more, and particularly preferably 90 mol% or more.

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 diesters of these aromatic dicarboxylic acids with C ₁ -C ₄ alcohols or C ₂ -C ₁₀ glycols. ;
Aliphatic dicarboxylic acids such as adipic acid and sebacic acid, or diesters of these aliphatic dicarboxylic acids with C ₁ -C ₄ alcohols or dihalf esters of C ₂ -C ₁₀ glycols; polyethylene oxide dicarboxylic acids, polypropylene oxide dicarboxylic acids An acid component such as a polyether dicarboxylic acid such as an acid or a diester with a C _{1 to} C ₈ alcohol or a dihalf ester with a C _{2 to} C ₁₀ glycol, ethylene glycol, propylene glycol,
Glycols such as butanediol, neopentyl glycol, p-xylidene glycol, 1,4-cyclohexanedimethanol; diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polyethylene oxide-polypropylene oxide copolymer glycol, etc. It is composed of an ester or a polyester component with a glycol component such as glycols.

As the metal sulfoaromatic dicarboxylic acid as the modifying component of the modified polyester, isophthalic acid containing a metal sulfonate group is preferable, the metal ion is an alkali metal such as sodium, potassium, lithium or cesium, and sodium is preferable. Specifically, 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid or their methyl esters, ethylene glycol half esters, and other The glycol half ester represented by 48 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%, and particularly preferably 3 to 6 mol%.

[0179]

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As the polyalkylene glycols useful as the modifying component of the modified polyester according to the present invention, polyethylene glycol is preferable, and the average degree of polymerization thereof is not particularly limited, but preferably 10 to 10,000, more preferably 20 to 8,000. , Particularly preferably 30 to 3,000. The content of the modified polyester of polyalkylene glycol is preferably 3 to 10% by weight, and more preferably 4 to 8% by weight, based on the total weight of the polyester.

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 preferred, and adipic acid is particularly preferred. 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 ⁹ OOCCH ₂ — (OCH ₂ CH ₂ ) _p —OCH ₂ COOR ¹⁰ Here, R ⁹ and R ¹⁰ are hydrogen or an alkyl group having 1 to 8 carbon atoms, and p 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 a plastic film can be used, and it may be copolymerized with other components or may be blended with other resins. The resin to be blended is preferably a polyester resin.

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

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

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

The laminated film useful in the present invention is characterized in that, when the thickness 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 (totally different layers), the order in which the layers are formed, the thickness, the constituents (the composition of the copolymerization). 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 Further, while observing the film under a microscope, each layer is scraped off, or the film is divided into halves, each of which is scraped from above and below to obtain an analyte of each of the upper and lower layers, and hydrolysis is performed to perform liquid chromatography and NMR.
It may be measured by various measuring devices such as, etc., or the analyte may be dissolved in a solvent and then NMR, GPC (gel permeation chromatography), intrinsic viscosity, etc. may be measured, or the analyte may be directly powdered. Can be mixed with X-ray spectroscope or KBr to measure IR (infrared spectrophotometer), etc., and as a result, it is asymmetrical in terms of absolute amount or peak position of measurement result, intensity difference, etc. Sex can be measured.

The modified polyester resin can be synthesized by the same method as the method for producing the aqueous copolyester. Therefore, the description of the synthesis method, the materials used, the additives, and the like accompanying it is omitted here.

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

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

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

The laminated film useful in the present invention has a structure in which two or more kinds of resin layers are laminated in three or more layers. A laminated film having a two-layer laminated structure is formed by combining such resin layers. Explaining with an example, it can be manufactured as follows. That is, for example, two kinds of resins are dried by two separate vacuum dryers, the respective resins are put into two separate 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 transverse stretching machine Stretched, a method of laminating a molten state to obtain a further subsequently thermally fixed biaxially stretched in the same cabin heat setting zone film, 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, an unstretched film or a uniaxially stretched film is separately prepared from two kinds of resins, and an anchor agent, an adhesive, etc. are coated on them, and then these two kinds of films are laminated and laminated, and then this is It is a method of axially stretching and heat setting. However, this method is not practical in terms of quality because the process is complicated and the equipment cost is too high, and the coextrusion method is preferable because of its simplicity.

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

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

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

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

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

The use of the support having the antistatic property coated with the antistatic composition is not limited to photographic films,
It can be widely used for drawing film, OHP film, marking film, animation film, etc.

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

In the case of 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 with respect to these supports is adopted. As the soluble or swellable solvent, acetone, methylene chloride, ethylene chloride, methanol, ethyl acetate,
Examples thereof include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoacetate, and dimethylformamide.

The undercoating method of the above-mentioned polyester film useful in the present invention can be applied by a polyethylene terephthalate undercoating method, and therefore 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. Pat.Nos. 2,852,378 and 358,6.
No. 08, No. 3,630,741, No. 2,627,088, No. 2,698,
235, JP-A-51-135991, JP-B-52-48312, Belgian Patent Nos. 721,469, 742,769 and the like, or vinylhalogenoester-containing copolymers or vinylhalogenoester-containing copolymers and vinyl chloride and / or vinylidene chloride. Containing Copolymer, Japanese Patent Publication No. 58-58661, Japanese Patent Publication No. 58-55497
JP-A-52-108114, copolymers containing a diolefin as a monomer, acrylic-based polymers described in JP-A-61-204242 and JP-A-61-204241, JP-B-5
Examples thereof include polyester polymers described in JP-A 7-971, JP-A 61-204240, JP-A 60-248231, JP-A 3-265624 and the like.

For the undercoating after the biaxial stretching heat setting, an organic solvent-based undercoating or a so-called etching solvent (for example, phenol, cresol, resorcin, or oxidizer) for adhering the undercoat material by anchoring effect by etching polyethylene terephthalate is used. 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 this surface structure is loose or chemically changed. For this, mechanical treatment, corona discharge treatment, flame treatment,
Surface activation treatment such as ultraviolet ray 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,
55-67745, JP-A-59-19941, etc., n-butyl methacrylate: quaternary copolymer latex composed of t-butyl methacrylate, styrene and 2-hydroxyethyl methacrylate, surfactant, curing agent Is coated with a water-based undercoating solution and dried, and then again subjected to corona discharge treatment,
Next, 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. Further, on the opposite side of the antistatic layer, the same treatment as above or an undercoat layer is applied, and then the antistatic composition is directly applied, and the antistatic layer binder such as cellulose diacetate is applied in advance and then the antistatic composition is applied. A desired photographic light-sensitive material can be finished by applying the product as an organic solvent system liquid.

<Antistatic Layer> An antistatic layer containing the π-electron conductive polymer of the present invention, an aqueous copolymer and a cross-linking agent (and an antiseptic agent if necessary) comprises an undercoat layer on a plastic film. It may or may not be interposed, but directly or indirectly, the π-electron conductive polymer, the aqueous copolymer and the crosslinking agent of the present invention (preservative as necessary).
It is obtained by applying an antistatic composition containing 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 subbing liquid and the antistatic 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. Patent 3,50
2, by 8,847, 2,941,898, 3,526,528, etc.
One or more layers may be coated at the same time, or a photographic light-sensitive material may be dipped in the composition of the present invention.

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

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

<Photosensitive 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 photographing, photographic light-sensitive material for printing, photographic for X-ray) is used. 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 light-sensitive layers is mainly made of gelatin, and the light-sensitive 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 crystal 〃 〃 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 Item IJ Desalting 995 Item IIA 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 III-A item 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.
The description location is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- Item C 25 to 26 XIII-C Light absorber 1003 VIII 25 to 26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25 to 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) Various couplers may be used. Yes, and specific examples thereof are also described in the above RD. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item 25 VII-C to G magenta coupler 1001 VII-D item 25 VII-C to G cyan coupler 1001 VII-D item 25 VII-C to G terms Colored coupler 1002 VII-G term 25 VII-G term DIR coupler 1001 VII-F term 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-
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided. Also, the aforementioned RD308119 VII-K
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section can be adopted.

The multilayer photosensitive layer is preferably applied in multiple layers using a slide hopper or a curtain coater.

To develop the photographic film of the present invention, for example, TH James, Theory of the Photographic Process 4th Edition (The Theory of The)
Photographic Process Forth Edition) Pages 291 ~ 334
Page and the Journal of the American Chemical Soc
well known developer described in Vol. 73, p. 3,100 (1951) can be used. Further, the color photographic light-sensitive material can be developed by the usual methods described in RD17643, pages 28 to 29, RDl8716, pages 615 and RD308119, XIX.

<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, 49-4503, U.S. Pat.Nos. 3,243,376, 3,220,843, etc., and the back surface of the photographic light-sensitive material, the amount of magnetic particles, size It is described in US Pat. Nos. 3,782,947, 4,279,945 and 4,302,523 that a transparent magnetic recording layer having the required transparency is provided by selecting the above. 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, various information on the photographic light-sensitive material such as the type / manufacturing number of the photographic light-sensitive material, the manufacturer name, the emulsion No. , Exposure time, lighting conditions, filter used, weather, size of shooting frame, camera model, use of anamorphic lens, and other various information at the time of camera shooting, for example, number of prints, selection of filter, customer Various information necessary for printing, such as the color preference and trimming frame size, for example, the number of prints,
Entering various information obtained at the time of printing such as filter selection, customer's color preference, trimming frame size, and other customer information is important for management and print quality improvement. It is convenient if the above-mentioned matters are recorded in order to improve the efficiency of printing work.

In a conventional photographic light-sensitive material, it is impossible to input all of this information. Therefore, at the time of shooting, information such as shooting date / time, aperture, exposure time, etc. is optically input. I was just there. Moreover, at the time of printing, it was completely impossible to input the above information into the photographic light-sensitive material because there was no means for that.

Since the magnetic recording method is easy to record / reproduce, the use of the magnetic recording method for inputting the above various information to the 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 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, barium ferrite magnetic powder, etc. are used. it can.

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

[0230]

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 The following plastic film was coated with the following undercoat layer and antistatic composition of the present invention to give an antistatic support, and a silver halide printing emulsion or the like was applied to these supports. Then, a silver halide photographic light-sensitive material was prepared and used for the test.

<Plastic film> A polyethylene terephthalate film having a thickness of 100 μm, which has been biaxially stretched and heat-set (indicated as PET as a support in Table 1), and also has a thickness of 80
μm polyethylene-2,6-naphthalate film (indicated as PEN in Table 1 as PEN), and 90 μm thick three-layer laminated film of the following modified polyester and polyethylene terephthalate (in Table 1, P / M / as support) (Denoted as P) were 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 product obtained was treated with 5-sodium sulfodi
Ethylene glycol solution of (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) 28 parts by weight (5 mol% / total acid content), polyethylene glycol (number average molecular weight 3000) 8.
1 part by weight (7% by weight / polymer), antimony trioxide 0.0
5 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.

<Synthesis of Comparative Aqueous Copolymer Compound FC-1) 0.53 mol of dimethyl terephthalate, 0.4 mol of dimethyl isophthalate, 0.07 mol of dimethyl sodium salt of 5-sulfoisophthalic acid, 0.003 of 1,3,5-methoxycarbonylbenzene.
1 mol, ethylene glycol 2 mol, zinc acetate dihydrate 0.1
A mixture of mmol and 0.01 mmol of antimony trioxide is stirred at 160 ° C. under a nitrogen stream, and methanol is allowed to flow out. When the outflow of methanol ceased, the temperature was gradually raised to 225 ° C over 3 to 4 hours, and while increasing the temperature to 255 ° C,
Reduce the pressure to 1 to 0.2 mmHg. Within 60 to 100 minutes, polycondensation occurs and a copolymer is obtained. The intrinsic viscosity of this aqueous copolymer was apparently 0.3-0.4 (not measurable due to the cross-linking of this composition). FC-1
And It was dispersed in hot water at 90 to 98 ° C. and used as a 30% by weight liquid.

<Formation of Subbing Layer / Preparation of Support> 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 dry film thickness 0.8. μm
Undercoating was applied to obtain a subbing 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.

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

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

Subsequently, a corona discharge of 8 W / m ² · min was applied on the undercoat layer B-1 and the undercoat layer A-1, and the following coating solutions b-2 and a-2 were formed on the respective layers. Dry film thickness 1.
The coating was applied so as to have a thickness of 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 support.

<< Coating Liquid b-2 (Antistatic Composition) >> Aqueous copolyester liquid (see Table 1) 540 g π-electron conductive polymer component (see Table 1) Weight to be 100 mg / m ² Crosslinker Table 1 Indicated weight Compound (C-6) 0.6 g Compound (C-7) 0.2 g Silica particles having an average particle diameter of 3 μm 0.1 g Water was made up to 1 liter.

<< 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.

[0243]

[Chemical 49]

<Preparation of photographic light-sensitive material for silver halide printing> 25 W / m ^{2 on} both sides of the above-mentioned undercoat layer A-2 and antistatic layer B-2 on the above-mentioned three types of undercoat and antistatic supports.・
Minute corona discharge, and the following back layer coating liquid b-3 and back layer protective layer coating liquid b-4 are formed on the antistatic layer B-2.
Was coated in two layers at a time so that the coated gelatin amounts were 2.0 g / m ² and 1.5 g / m ² , respectively, to give back layer B-4. On the other hand, an emulsion layer (coating gelatin amount: 2.0 g / m ² ) was coated with the following emulsion layer coating liquid formulation on the subbing layer A-2, and an emulsion protective layer (coating gelatin amount: 1.0 g / m ² ) was further formed thereon. Were simultaneously coated in two layers and dried to prepare a photographic light-sensitive material for silver halide printing, which was then subjected to a test.

<Formation of Back Layer and Photosensitive Layer><< Preparation of Back Layer Coating Liquid b-3 >> 36 g of gelatin was swelled in water and dissolved by heating, and then the compound (C-1) was used as a dye.
1.6 g, compound (C-2) 310 mg, compound (C-3) 1.9
g, and 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.

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[0247]

[Chemical 51]

<< 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. Furthermore, spherical polymethylmethacrylate having an average particle diameter of 4 μm was added as a matting agent so as to have a concentration of 40 mg / m ² ,
Coating liquid for protective film layer b-
4 was prepared.

<< Preparation of Silver Halide Emulsion Layer Coating Solution for Printing >><< Preparation of Silver Halide Emulsion Coating Solution >> After adding 9 mg of 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 added sequentially, 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 containing 2 mol% of silver bromide was prepared as follows. Silver nitrate 60
An aqueous solution containing 23.9 mg of pentabromorhodium potassium 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 6 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.

[0254]

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[0255]

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

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

Fixer Formulation (Fixing Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid ( 90% W / W aqueous solution) 8.1 ml (Fixing composition B) Water 17 ml Sulfuric acid (50% W / W aqueous solution) 5.8 g Aluminum 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.

<Evaluation of Antistatic Performance><< Ash Adhesion Test >> Two samples of 10 cm square were cut out, exposed, and subjected to the above development treatment under the above conditions.
Humidity was adjusted for 24 hours in an atmosphere of 23 ° C. and 40% RH, and the test was performed. The exposed and developed sample was placed on a rubber plate with the emulsion side up, and the emulsion side was charged by rotating the rubber roller 10 times. One minute later, the cigarette ash prepared separately was densely and evenly spread on the paper, and the sample (with the emulsion side facing down) was clamped at both ends with clips of an insulating material in the upper space where it was vertically spread out. The antistatic effect was evaluated by evaluating the degree of adhesion of ash to the sample by using a simple device in which the surface of the sample was positioned parallel to the plane of the ash by the worm gear and lowered in parallel. 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 and removes them to prevent static electricity from leaking from the hand holding the sample.

Evaluation level A: Level at which the sample does not adhere to ash at all B: When the sample comes into contact with ash, ash adheres to the sample, but when the distance between the sample and ash is 1 cm, ash does not exist at all. Level of non-adhesion C: Ash adheres when the distance between the sample and ash is 1 cm, but 2
Level that does not adhere at a distance of cm D: Ash adheres when the distance between the sample and ash is 2 cm, but 4
Level that does not adhere at a distance of cm E: Ash adheres when the distance between the sample and ash is 4 cm, but 6
Level that does not adhere at a distance of cm F: Ash adheres even if the distance between the sample and ash is 6 cm, but 8
Level that does not adhere at a distance of cm G: Ash adheres even if the distance between the sample and ash is 8 cm, but 10
Level that does not adhere at a distance of cm H: Level at which ash adheres even if the distance between the sample and ash is 10 cm or more.

Since all the results of the ash adhesion test were good, the data are not shown in Table 1 and are omitted.

<Coatability test> b on the antistatic layer B-2
-5 was applied to prepare a back layer B-3 sample having a length of 150 cm in the width direction of the support and a length of 30 cm in the machine traveling direction, and 5 samples were prepared. Regarding the coating property, coating nonuniformity such as liquid deviation and tail defects, etc. were placed on a Schaukasten and observed through the light of a white fluorescent lamp. 10 when observing a tail-shaped defect
Use double loupe. The evaluation levels are as follows.

<< Evaluation of Non-uniformity of Uniform Application from Liquid >> AA: None at all from the liquid A: Appeared to be uniformly applied without any shade of color from the liquid B: There is a slight shade of color Visible C: Rough wide band-like light and shade is slightly visible D: Rough band-like light and shade is visible E: Light and dark on one side is clear.

<< Evaluation of Tail-like Defects, etc. >> A: No small particles, no tail-like particles, etc. B: Very small particles such as very small particles are seen. C: Small particles, or tail-like color. You can see a few things that are different D: Small granules and those with different tail-bowl colors are seen E: Many granules and those with a different tail-bill color are seen .

<Test with Film> A photographic light-sensitive material sample for silver halide printing was conditioned in a room at 23 ° C. and 55% RH for 24 hours, and the sample was placed in a barrier bag laminated with an aluminum foil with a black polyethylene film. After heating in an oven at 40 ° C for 3 weeks, cooling, opening, and taking out the sample, the undeveloped dry film test of the back layer and the processed dry film, and the undeveloped wet film test and the processed wet film, respectively The attached test was conducted. The method of heating with a barrier bag is for accelerating prediction of the performance of the product during its effective period.

<< Dry Film Test >> A photographic photographic material sample for developed silver halide printing having a size of 20 cm × 20 cm reached the plastic film surface slightly with a razor with the back layer surface at an angle of 45 ° from the horizontal plane. To length 30
scratched mm. Then, in an atmosphere of 23 ° C and 80% RH, 24
After conditioning the humidity for a period of time, at a right angle,
A cellophane tape with a width of mm (cellophane tape manufactured by Nichiban Co., Ltd., a registered trademark) is attached about 50 mm in length and rubbed and adhered with a rounded corner plastic. The end of the cellophane tape was held almost parallel to the sample surface on the side opposite to the 45 ° scratch, and was pulled and pulled off rapidly. Regarding the peeled area of the back layer, the peeled area of the film surface was examined and evaluated as follows.

A: Not peeled off at all B: Some scratches were peeled off, and the peeled area was the entire area.
Less than 10% peeled off C: Peeled area 10% or more and less than 50% peeled D: Peeled area 50% or more and less than 80% peeled E: Peeled area more than 80% slightly left Exfoliated as much as possible F: There was almost no resistance to exfoliation, and exfoliation was complete.

Table 1 shows the results with a dry film.

[Test with wet film] A sample of 20 cm x 20 cm
Samples of the same size are immersed in the developing solution for the specified time under the above conditions for a predetermined time, and the back layer surface remains sharp before the drying process for the entire time of the developing process. It was rubbed with a fingertip with a rubber glove scratched on the entire surface of the grid, and the peeled area of the back layer was examined and evaluated as follows.

A: Not peeled off at all B: Peeling around the scratch was very slight C: Peeling around the scratch was 10% or less of the total area D: Peeling area was 10% or more and less than 50% E: The peeled area was separated by 50% or more and less than 80% F: The peeled area was peeled by 80% or more by a small amount G: The whole area was peeled or more was peeled.

Table 1 shows the results with a wet film.

<Melting Time Test> The sample coated with the back layer was conditioned in a room at 23 ° C. and 55% RH for 24 hours,
Place the sample in a barrier bag laminated with aluminum foil with a black polyethylene film, and place it in an oven at 40 ° C for 3 days.
After warming for a week, let it cool, open and remove the sample.
The sample coated with the emulsion in 1.5% aqueous sodium hydroxide solution (3 cm x 8 cm, passed through a hanging wire for hanging a hole at one end in the long side direction) was dipped for about 3/5 to form a back layer. The time until peeling was measured. The upper limit is 60
Seconds, no further measurement. The results are shown in Table 1.

[0273]

[Table 1]

<Evaluation and Results> In the ash adhesion test, the evaluation levels of the present invention and each comparative sample were good (A). Further, as is clear from Table 1, the sample without the cross-linking agent had a slightly higher coating property than the liquid, but with the film, there was a large difference between with and without the cross-linking agent. The difference is large. There is a correlation between the wet film and the melting time, and the film with a melting time of about 10 seconds has a very bad film. As described above, it was found that the combination of the π-electron conductive polymer, the aqueous copolyester and the crosslinking agent of the present invention exhibits excellent performance.

[Example 2] <Bacterial culture test of antistatic composition> <Preparation of culture test composition> π-electron conductive polymer component (see Tables 2 and 3) 10 g Preservative (see Tables 2 and 3) 4 g or no addition Aqueous copolyester (see Tables 2 and 3) 50 g Cross-linking agent Weight shown in Tables 2 and 3 100 ml was prepared with water.

<< Bacteria culture test (dishes test) >>
A fixed amount of the above-mentioned culture test composition of the present invention and the comparative test composition was placed on a petri dish, and the petri dish was covered with a lid, and incubated for 3 weeks in an environment of 35 ° C and 80% RH. After each incubation, the dish was taken out and the number of colonies generated was counted. In addition, although the occurrence of colonies is not clear, if it feels like a very small number,
? I put a mark.

The comparative compounds of preservatives are shown below.

[0278]

[Chemical 54]

Results of bacterial culture test Tables 2 and 3
It was shown to.

[0280]

[Table 2]

[0281]

[Table 3]

<Evaluation and Results> As can be seen from Tables 2 and 3, the composition of the π-electron conductive polymer, the aqueous copolyester and the cross-linking agent of the present invention has the general formula (I) and / or
Alternatively, as a result of a bacterial culture test in which a preservative of the general formula (II) was added, no colonies were observed, indicating that the antiseptic effect of the present invention is excellent. It should be noted that the presence of the crosslinking agent has a slight suppressing effect on the generation of colonies.

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 obtain 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 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 antistatic composition described below. a
-10 (the antistatic composition immediately after preparation and the antistatic composition stored at 25 ° C. for 3 weeks after preparation) and b-10 were coated on both surfaces to form subbing layers A-10 and B-10 (film after stretching). It was applied so that the thickness 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. Then, both surfaces of the subbing layers A-10 and B-10 were subjected to a corona discharge treatment of 8 W / m ² · min, and the subbing solution a was applied to both sides.
Undercoat layers A-11 and B-11 were coated on -11 and b-11 so that the dry film thickness was 0.8 μm.

<< In-line Antistatic Subtraction Liquid a-10 and b-10 Formulation >> Aqueous copolyester liquid (see Tables 4 and 5) 540 g π-electron conductive polymer component (see Tables 4 and 5) 100 mg / m ² Weight of crosslinker Weight shown in Tables 4 and 5 Weight of preservative 35 mg / m ² Weight of compound (C-6) 0.6 g Compound (C-7) 0.2 g Silica particles with an average particle size of 3 μm 0.1 g Water 1 liter Finished.

<< Preparation of Subbing Solution a-11 >> Gelatin 10 g Compound (C-6) 0.2 g Compound (C-7) 0.2 g N, N ′, N ″ -trisacryloyl-1,3,5-trimethylene Triamine 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Water is made up to 1 liter.

<< Preparation of Subbing Solution b-11 >> Gelatin 20 g Compound (C-6) 0.2 g Compound (C-7) 0.2 g N, N ′, N ″ -trisacryloyl-1,3,5-trimethylene Triamine 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Water is made up to 1 liter.

The following light-sensitive layer was coated on the above A-11 and B-11 to prepare a silver halide X-ray photographic light-sensitive material.

<Preparation of silver halide X-ray photographic film><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 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
20 g of O ₄ was added per 1 mol of AgX, the mixture was left to stir 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.

[0292]

[Chemical 55]

The obtained emulsion was chemically sensitized as follows. 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, diethylene glycol 5 g, nitrophenyl-triphenylphosphonium chloride 50 mg, 1,3-dihydroxybenzene-4-sulfonic acid ammonium 4 g, 2-mercaptobenzimidazole-5-sulfonic acid sodium 15 m
g,

[0296]

[Chemical 56]

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.)

[0299]

[Chemical 57]

Further, 30% by weight of the above 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.

The following tests were conducted on each of the obtained samples.

<Evaluation of Antistatic Performance><< Ash Adhesion Test >> An ash adhesion test was performed on the developed film in the same manner as in Example 1, but the antistatic composition was stored at 25 ° C. for 3 weeks after preparation of the antistatic composition. A sample using the coated substrate was tested. The results are shown in Tables 4 and 5.

<Spark Detection Test> After preparation of the antistatic composition, it was stored at 25 ° C. for 3 weeks and the sample using the support coated with the antistatic composition was conditioned at 23 ° C. and 40% RH in a dark room. A rubber roller was placed on a rubber plate in the same manner as in Example 1, and 10 rotations were performed on an unexposed sample whose humidity was controlled under the same conditions.
The degree of spark trace generation and rank are shown below by a method of generating static electricity and developing the sample to observe the degree of spark generation.

A: There is no trace of sparks in the sample area B: Something is not clear like a spark in the sample area C: There is one very small spark trace in the sample area D: Of the sample area Several small spark traces are seen inside E: There are considerable spark traces in the sample area F: There are spark traces on the entire sample area G: There are spark traces on the entire sample area.

The development of the above sample was performed by using an SRX-501 automatic developing machine (manufactured by Konica Corporation) with an XD-SR developer.
It was treated for 45 seconds.

The test results are shown in Tables 4 and 5.

<Coatability test> 25 ° C. after preparation of antistatic composition
Samples using the support coated with the antistatic composition stored for 3 weeks were tested. Prepare 5 samples each with a length of 150 cm in the width direction of the support and a length of 30 cm in the machine moving direction, and place all 5 samples on the Schaukasten for tail-like defects etc. It was observed through the light of a white fluorescent lamp. Use a 10x magnifying glass to observe tail-shaped defects. The evaluation levels are as follows.

<< Evaluation of Tail-like Defects >> A: There are no small particles or tails B: Very small particles such as very small particles are seen C: Small particles or tail-like color You can see a few things that are different D: Small granules and those with different tail-bowl colors are seen E: Many granules and those with a different tail-bill color are seen .

The results are shown in Tables 4 and 5.

<Melting Time Test> A sample using the support coated with the antistatic composition, which was stored at 25 ° C. for 3 weeks after preparation of the antistatic composition, was heated in the same manner as in Example 1 to give an example. It tested on the same conditions as 1. The results are shown in Tables 4 and 5.
It was shown to.

<Test with Wet Film> A sample using the support coated with the antistatic composition, which was stored at 25 ° C. for 3 weeks after preparation of the antistatic composition, was heated as in Example 1 to give X.
A test with a wet film was performed while wet in the final step of D-SR developer treatment. The results are shown in Tables 4 and 5.

[0314]

[Table 4]

[0315]

[Table 5]

As is clear from Tables 4 and 5, the samples to which the preservative of the present invention was added did not deteriorate in coating property, charging performance, wet film formation and melting time even after storage for 3 weeks. It was found to have excellent performance.

[Example 4] <Preparation of inline undercoating antistatic processed polyethylene-2,6-naphthalate support> Inline undercoating antistatic processed polyethylene-in the same manner as inline undercoating of polyethylene terephthalate of Example 3. A 2,6-naphthalate support was prepared as follows. Commercially available photographic grade polyethylene-2,6-naphthalate resin chips with an intrinsic viscosity of 0.63 were vacuum dried at 150 ° C for 8 hours, then introduced into an extruder and melted, and melt-extruded in layers from a T-die at 290 ° C. Rotating 5
The resin sheet was adhered to the cooling drum at 0 ° C. while applying static electricity, and rapidly cooled and solidified to form an unstretched sheet. Subsequently, this unstretched sheet was subjected to a roll-type longitudinal stretching process at 95 ° C. in a longitudinal direction of 3.5 ° C. A uniaxially stretched film obtained by stretching twice the film was then continuously coated with the following in-line undercoating antistatic compositions a-20 and b.
-20 is coated on both sides to form an undercoating antistatic layer A-20 and B-20
(Coating so that the film thickness after stretching is 0.1 μm). Further, 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 biaxially stretched film having a thickness of 90 μm. Then, both surfaces of the undercoating antistatic layers A-20 and B-20 were subjected to corona discharge treatment of 8 W / m ² · min, and the undercoating liquids a-21 and b-21 were dried on both surfaces to a dry film thickness of 0.8 μm.
And gelatin subbing layers A-21 and B-21 were coated.

<< Inline Undercoating Antistatic Composition a-20 and b-20 Formulation >> Aqueous copolyester liquid (see Tables 7 and 8) 540 g π-electron conductive polymer component (see Tables 7 and 8) 100 mg / m ² Weight of the cross-linking agent Weight shown in Tables 7 and 8 Compound (C-6) 0.6 g Compound (C-7) 0.2 g Silica particles having an average particle size of 3 μm 0.1 g Water was made up to 1 liter.

<< Preparation of Subbing Solution a-21 >> Gelatin 10 g Compound (C-6) 0.2 g Compound (C-7) 0.2 g N, N ′, N ″ -trisacryloyl-1,3,5-trimethylene Triamine 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Water is made up to 1 liter.

<< Preparation of Subbing Liquid b-21 >> Gelatin 20 g Compound (C-6) 0.2 g Compound (C-7) 0.2 g N, N ′, N ″ -trisacryloyl-1,3,5-trimethylene Triamine 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Water is made up to 1 liter.

<Preparation of silver halide color photographic light-sensitive material> A silver halide color photographic light-sensitive material was prepared by coating the following emulsion layers on A-21 and a magnetic recording material layer on B-21. Created.

<< Coating of multi-layer color emulsion layer and the like >> A-21 of the above-mentioned processed polyethylene-2,6-naphthalate film
After a corona discharge of 25 W / (m ² · min) was applied on the surface, a multilayer color photographic constituent layer was sequentially coated from the first layer.

The coating amount in the photographic constituent layers shown below is the amount expressed in units of g / m ² 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 << Third layer: low-sensitivity red-sensitive layer >> Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD-2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 Sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (Di-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 << Fourth layer: Medium-sensitive red-sensitive layer >> Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 Sensitizing dye (SD-2) 0.86 × 10 ^-4 Sensitizing dye (SD-3) 1.15 × 10 ^-5 Sensitizing dye 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 0.7
9 << Fifth layer: high-sensitivity red-sensitive layer >> Silver iodobromide emulsion D
0.95 Sensitizing 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 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 << Sixth layer: Intermediate layer >> Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 << Seventh layer : Low sensitivity green sensitive layer >> 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 << 8th layer: Intermediate layer >> Gelatin 0.41 << 9th layer: Medium sensitivity green-sensitive layer "silver iodobromide emulsion B 0.30 silver iodobromide emulsion C 0.34 sensitizing dye ^{(SD-6) 1.2 × 10} -4 sensitization Arsenide (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 solvent (OIL-4) 0.12 gelatin 0.50 "10th layer: high sensitivity green-sensitive layer" iodobromide emulsion D 0.95 sensitizing dye (SD-6) 7.1 × 10 - ⁵ Sensitizing dye (SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD-8) 7.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-) 4) 0.11 Gelatin 0.79 << 11th layer: Yellow filter layer >> Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 << 12th layer: Low sensitivity blue sensitive layer >> Iodobromide Silver emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitized color Element (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 sensitive layer >> Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 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 Slip agent (WAX-1) 0.04 In addition to the gelatin 0.55 Note the composition, coating aid Su-1, dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of polyvinylpyrrolidone having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and a preservative compound (A) were added.

The 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.

[0326]

[Table 6]

[0327] The sample was coated with a multi-slide hopper type coater at the first time, from the first layer to the eighth layer, and at the second time, onto it from the ninth layer to the fifteenth layer, respectively.
The specific photographic speed was ISO420. The structure of each compound used for the preparation of the sample is shown below.

[0328]

Embedded image

[0329]

Embedded image

[0330]

Embedded image

[0331]

[Chemical formula 61]

[0332]

Embedded image

[0333]

[Chemical formula 63]

[0334]

[Chemical 64]

[0335]

Embedded image

[0336]

[Chemical formula 66]

<< Coating of Magnetic Recording Material >> The following magnetic recording layer coating solution c- was applied to each B-21 surface of the film of polyethylene-2,6-naphthalate subjected to the above-mentioned undercoating and antistatic treatment on the side opposite to the photosensitive layer. 1 to a dry film thickness of 1.0 μm,
Each of the magnetic recording layers was C-22.

<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 and then cooled, and then 75 parts by weight of cyclohexanone and 150 parts by weight of methyl ethyl ketone were mixed therein, 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.

<Development Processing> The development processing of the color photographic film sample was carried out 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 Water is added to make 1 liter (pH = 10.1).

<< Bleaching Solution >> 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 is adjusted to 6.0 with acetic acid.

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

<Antistatic Performance Evaluation Method><< Ash Adhesion Test >> A sample having the same dimensions as in Example 1 was prepared, the humidity was adjusted in the same manner, the sample was sealed in a barrier bag, heated at 40 ° C. for 3 weeks, and then opened by cooling. Then, an ash adhesion test was conducted under the same conditions as in Example 1. The results are shown in Tables 7 and 8.

<< Peel off static test >> 35 samples were placed in a dark room.
Cut into a size of mm width and length of 1 m, adjust the humidity of the film in a dark room environment of 23 ° C. and 80% RH, tape the end of the film to the 40 mm core with tape, wind the photosensitive layer inside, and end Tape and seal the rolled film in a sealed can.
It was heated in an oven at ℃ for 24 hours, opened at 23 ℃, 20% RH in a dark room environment, peeled off, and immediately developed to examine the degree of color development due to yellow static electricity in the blue sensitive layer. The degree of color development was ranked as follows.

A: No color development B: A slight part of what seems to be color is felt in a very small part C: There are 1 or 2 slightly small color development points in the entire length D: Color development over the entire length Spots are slightly scattered E: Coloring points are scattered over the entire length F: Coloring is considerably observed G: Coloring is entirely observed.

<Test with Wet Film> The color photosensitive layer and the magnetic recording layer (C-22) were tested with a wet film. The test method was the same as in Example 1, and the sample was subjected to a heating treatment in a barrier bag at 40 ° C. for 3 weeks in the same manner as in Example 1 and subjected to the test. The results are shown in Tables 7 and 8.

<Melting Time Test> The color photosensitive layer sample and the magnetic recording layer sample were separately subjected to the melting time test. The measurement method is the same as that in Example 1, and each sample is the same as in Example 1, which is heated at 40 ° C. for 3 weeks in a barrier bag. The results are shown in Tables 7 and 8.

[0350]

[Table 7]

[0351]

[Table 8]

<Evaluation and Results> As can be seen from Tables 7 and 8, the composition containing the crosslinking agent of the present invention shows little difference in antistatic performance from the comparative example, but both with wet film and with melting time. Excellent results have been obtained. Further, in the comparative example, the magnetic recording layer had a wet film and the melting time was poor.

[0353]

EFFECTS OF THE INVENTION A cross-linking agent is used to prevent the antistatic composition of a silver halide photographic light-sensitive material having a layer formed by applying an antistatic composition containing a π-electron conductive polymer and an aqueous copolyester. By including it in the composition,
It is possible to make stable and excellent products. Further, by incorporating a kind of preservative into the antistatic composition, it was possible to improve the instability in production and also to improve the deterioration of the antistatic performance.

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

Claims (5)

[Claims] 1. A plastic film having an antistatic layer containing a π-electron conductive polymer, an aqueous copolyester and a crosslinking agent on at least one side, and at least one silver halide emulsion layer on at least one side. A silver halide photographic light-sensitive material characterized by having. 2. The π-electron conductive polymer is polypyrrole and its derivative, polythiophene and its derivative, polyfuran and its derivative, polyaniline and its derivative, poly
(2,5-thienylene vinylene) and its derivatives, polyisothianaphthene and its derivatives, thiophene and pyrrole copolymers and their derivatives, polyparaphenylene vinylene and its derivatives, polyselenophene and its derivatives, and these 2. The silver halide photographic light-sensitive material according to claim 1, wherein the π-electron-type conductive polymer is a branched polymer linked to another chain polymer. 3. The halogen according to claim 1 or 2, wherein the aqueous copolyester is a copolyester containing an aromatic dicarboxylic acid having an alkali metal salt sulfonate group as a modifying component of the copolyester. Silver halide photographic light-sensitive material. 4. The aqueous copolyester is a copolyester containing an aromatic dicarboxylic acid having an alkali metal salt sulfonate group and polyethylene glycol having an average degree of polymerization of 30 to 3000 as a modifying component. The silver halide photographic light-sensitive material according to claim 3. 5. The antistatic layer according to claim 1, further comprising a compound represented by the general formula (I) and / or the general formula (II). Silver halide photographic light-sensitive material. Embedded image Embedded image In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group, a cyclic alkyl group, an aryl group,
It represents a cyano group, an alkylthio group, an arylthio group, an alkyl sulfoxide group, an alkylsulfonyl group or a heterocyclic group. However, the alkyl group, cyclic alkyl group, alkenyl group, heterocyclic group, aralkyl group and aryl group may have a substituent. A ring may be wound around R ¹ and R ² . R ³ is a hydrogen atom, a linear or branched alkyl group,
It represents a cyclic alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkylamide group, an arylamide group, an alkylthioamide group, an arylthioamide group and an alkylsulfoamide group. In the formula, R ⁴ is a hydrogen atom,
It represents a lower alkyl group or a hydroxymethyl group, and R ⁵ and R ⁶ represent a hydrogen atom or a lower alkyl group.