JPH09211787A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material showing no deterioration in physical properties while maintaining the conductivity after development by incorporating a polyacrylate-epoxy crosslinked material into at least one hydrophilic colloid layer. SOLUTION: One hydrophilic colloid layer contains a polyacrylateepoxy crosslinked material. As for the polyacrylate and its salt, a compd. having 10000 to 1000000 weight average mol.wt. is preferable, and a compd. having 50000 to 500000mol.wt. is especially preferable. As for the counter cation to form a salt, alkali metals, alkaline earth metals, and org. amines can be used, and alkali metals and orb. amines are preferable, and lithium, potassium and sodium are especially preferable. As for the hydrophilic colloid, gelatin is especially preferable. Either alkali-treated gelatin or acid-treated gelatin can be preferably used. The amt. of the gelatin is preferably 1 to 15g/m<2> , especially 1.5 to 13g/m<2> considering flatness and drying property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which has conductivity even after development and has excellent physical properties.

[0002]

2. Description of the Related Art Generally, a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) is provided with conductivity in order to cope with static electricity generation represented by friction in a camera. Furthermore, it is preferable that the conductivity is maintained after the development process because of handling such as printing on photographic paper and editing.

JP-A-55-95942 discloses a cross-linking technique using a carboxy group-acting hardener containing polyacrylic acid. However, it was difficult to maintain the conductivity even after the development processing only by this technique. Further, even if it can be maintained, there is a defect that the physical properties of the light-sensitive material are weak and are easily damaged.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which maintains conductivity even after development and does not deteriorate in physical properties.

[0005]

[Means for Solving the Problems]

(1) A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers contains a polyacrylic acid-epoxy crosslinked body. A silver halide photographic light-sensitive material.

(2) In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, at least one of the hydrophilic colloid layers is at least one selected from polyacrylic acid and salts thereof. A silver halide photographic light-sensitive material containing a seed and being hardened with at least one selected from an epoxy hardener and a carboxyl group active hardener.

(3) The silver halide photographic light-sensitive material as described in (1) or (2), which has a conductive layer between the hydrophilic colloid layer and the support.

(4) In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, at least one of the hydrophilic colloid layers is at least one selected from polyacrylic acid and salts thereof. A silver halide photographic light-sensitive material containing a seed and having a conductive layer between the support and the support.

(5) In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least two layers of polyacrylic acid and a salt thereof on a support, the hydrophilic colloid layer is Among them, the amount of at least one selected from polyacrylic acid and its salt contained in the hydrophilic colloid layer present in the position closer to the support is the polyacrylic acid contained in the hydrophilic colloid layer present in the position farther from the support. A silver halide photographic light-sensitive material characterized in that the amount is at least one selected from the salt.

Hereinafter, the present invention will be described in detail.

The polyacrylic acid and salts thereof used in the present invention have a weight average molecular weight of 10,000 to 1,000.
000 is preferable, and 50,000 to 500,000 is particularly preferable. Examples of the counter cation for forming a salt include alkali metals, alkaline earth metals and organic amines, with alkali metals and organic amines being preferred and lithium, potassium and sodium being particularly preferred.

In the present invention, gelatin is particularly preferable as the hydrophilic colloid. As the gelatin, both alkali-treated gelatin and acid-treated gelatin can be preferably used. When using ossein gelatin, it is preferable to remove calcium and iron.

Examples of other hydrophilic colloids include water-soluble polymers such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and dextran sulfate.

In the present invention, the amount of gelatin used in the hydrophilic colloid is 1 to 15 from the viewpoint of flatness and drying property.
preferably g / m ^2, particularly preferably 1.5~13g / m ^2.

Also, the swelling rate of the hydrophilic colloid is preferably 200 to 300%, and particularly preferably 210 to 290% from the viewpoints of flatness and dryness. The swelling ratio is a value calculated by obtaining the amount of water absorption per 1 g of hydrophilic colloid at 38 ° C. for 3 minutes by the following formula.

Swelling rate (%) = 100+ (water absorption amount / back surface layer weight) × 100 In the present invention, the content of polyacrylic acid and its salt in the hydrophilic colloid layer is 1 to 80% by weight based on the whole binder. Is preferred and 5 to 50% by weight is more preferred.

The polyacrylic acid used in the present invention can be used as a copolymer with other monomers, but the above-mentioned contents are required as acrylic acid and its salt.

In the hydrophilic colloid layer containing polyacrylic acid of the present invention, when polyacrylic acid is contained in two or more hydrophilic colloid layers, if the total content is the same, the side of the support far from the support is We have found that when the hydrophilic colloid layer contains more polyacrylic acid, the deterioration of physical properties can be suppressed.

The ratio in the case of containing two or more layers can be arbitrarily selected, but the amount contained in the layer distant from the support: the amount contained in the layer close to the support = It is preferably 1: 0.99 to 10: 1.

In the present invention, the carboxyl group-activating type hardener is not particularly limited, but is disclosed in JP-B-58-326.
99, JP-A-63-229450, 62-828.
The compounds described in No. 54, No. 63-41580 and the like can be used.

In the present invention, the epoxy hardener used as a hardener has a molecular weight of 100 to 150.
Those having an epoxy equivalent of 100 to 300 are preferable.

Preferred specific examples of the epoxy hardener are shown below.

[0023]

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[0024]

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In the present invention, the epoxy hardener is 0.0 per 1 g of gelatin contained in the hydrophilic colloid layer.
It is preferably used in the range of 01 to 0.5 g, and more preferably 0.002 to 0.3 g.

As a method of curing the hydrophilic colloid layer with an epoxy hardener, a method of adding an epoxy hardener to the coating liquid in advance, or a method of simultaneously adding the epoxy hardener during the coating of the coating liquid is used. There are a method of adding and a method of applying an epoxy type hardener after the application of the coating solution and before the completion of drying. In the present invention, any of these can be preferably used.

The silver halide emulsion layer contained in the color light-sensitive material of the present invention preferably contains a lipophilic photographic additive. Examples of lipophilic photographic additives include couplers, high-boiling point organic solvents, UV absorbers, formalin scavengers, etc., but particularly when couplers and high-boiling point organic solvents are used, the effect of the present invention is remarkable. is there.

As the coupler, Research Disclosure (hereinafter abbreviated as "RD") 308119, page 10
The couplers described in 01 to 1002 and RD17643 can be mentioned.

The relevant parts of the RD are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C to G magenta coupler 1001 VII-D item VII C to G item Colored coupler 1002 VII-G item VII G item DIR Coupler 1001 VII-F item VII F item BAR coupler 1002 VII-F item Other useful residues 1001 VII-F item Release coupler Alkali-soluble coupler 1001 VII-E item As a high-boiling point organic solvent, a boiling point of 130 ° C or higher, 400 ℃
The following are preferable, and further 150 ° C. or higher, 350
C. or lower is preferred.

Concretely, phthalic acid esters such as dioctyl phthalate, phosphoric acid esters such as tricresyl phosphate, epoxy compounds described in JP-A-5-97099 and 5-119448, and JP-A-4-265975. Examples thereof include alcohols and amides described in JP-A-5-188547.

In the present invention, it is preferable to have a further conductive layer between the hydrophilic colloid layer containing polyacrylic acid or a salt thereof and the support. Conductive layer in the present invention, the effect of the present invention can be obtained higher in the case of 10 ¹² [Omega] cm or less under the conditions of the surface resistivity value of 23 ° C. 20% RH, still 10 ¹¹ [Omega] cm or less when the effect Is big. The smaller the surface resistivity, the greater the effect of the present invention, but due to the nature of the compound, it is 10 ⁵ Ωcm or more.

As the conductive layer, a conductive layer containing metal oxide particles, a conductive layer containing a reaction product of a water-soluble conductive polymer and a crosslinking agent, and a conductive layer containing a π-electron conductive polymer. A conductive layer and a conductive layer containing a polymer ionic solid electrolyte.

The metal oxide particles used in the present invention include:
Those containing oxygen vacancies and those containing a small amount of a different atom forming a donor with respect to the metal oxide used are generally preferred because they have high conductivity. In particular, the latter does not give fog to silver halide emulsions. Therefore, it is preferable.

Examples of metal oxides are ZnO, V ₂ O ₅ ,
TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , M
gO, BaO, MoO ₃ or the like or a composite oxide thereof is preferable, and ZnO, TiO ₂ , V ₂ O ₅ and SnO ₂ are particularly preferable.

As an example containing a heteroatom, for example, ZnO
For Al, In, etc., and SnO ₂ for S
It is effective to add b, Nb, a halogen element or the like, and to TiO ₂ , add Nb, Ta or the like. The addition amount of these heteroatoms is preferably in the range of 0.01 to 3.0 mol%, and particularly preferably 0.1 to 10 mol%.

The usable particle size is preferably 10 μm or less, but when it is 2 μm or less, the stability after dispersion is good and it is easy to use. Also, in order to minimize the light scattering property,
It is particularly preferable to use metal oxide particles of 0.5 μm or less because a transparent photosensitive material can be formed. These particles may be in a sol state as described in JP-A-6-59392.

The metal oxide particles used in the present invention are manufactured mainly by the following method. First, a method of producing metal oxide fine particles by firing and performing heat treatment in the presence of a different atom that improves conductivity, and second, for improving conductivity when producing metal oxide fine particles by firing. And a method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing the metal fine particles by firing are easy.

The first method can effectively improve the conductivity of the fine particle surface, but grain growth may occur during the heat treatment, so it is necessary to select conditions. Further, it may be better to perform the heat treatment in a reducing atmosphere.

The second method is preferable because it seems that the manufacturing cost is the lowest. For example, it is the hydrate of SnO ₂ beta-stannic acid colloids in the process of obtaining a SnO ₂ fine particles by spraying a (amorphous) in a firing furnace, SbCl ₃ in beta-stannic acid colloids, Sb (NO ₃₎ Conductive SnO ₂ fine particles can be obtained by coexisting ₃ , Sb ₂ O ₃ hydrate and the like. Further, as another example, in a so-called gas phase method in which SnCl ₄ and TiCl ₄ are oxidatively decomposed to produce SnO ₂ and TiO ₂ , when SnO ₂ and TiO ₂ which are salts of different atoms are coexistent during oxidative decomposition, conductive SnO ₂ and TiO _{2 are obtained} . You can get ₂ .

In addition, in the method of thermally decomposing an organic acid salt of a metal to obtain a metal oxide, there is also a method of allowing salts of different metals to coexist during the thermal decomposition.

As an example of the third method, in a vacuum evaporation method in which a metal is evaporated in an oxygen atmosphere to obtain metal oxide fine particles, a method of keeping the amount of oxygen inadequate, or insufficient supply of oxygen There is a method of heating metals and metal salts.

In the present invention, the conductive metal oxide particles may be crystalline or amorphous.

In the present invention, conventionally known polymers can be used as a part or all of the binder in the conductive layer. Examples of these compounds include gelatin, polyvinyl alcohol, polyvinylbenzene sulfonates, polyvinylbenzyltrimethylammonium chloride, U.S. Pat. Nos. 4,108,802 and 4,118,
No. 231, No. 4,126,467, No. 4,137,2
No. 17, etc., quaternary salt polymers, US Pat.
0,189, OLS 2,830,767 (USSe
r. No. 816, 127) and the like, crosslinked polymer latexes, polyacrylic acid, polyacrylamide, dextrin and the like.

The amount of conductive particles used is 1 m ² of the photographic light-sensitive material.
0.05 to 20 g is preferable, and 0.1 to 10 g is particularly preferable.

In order to use the metal oxide particles more effectively and lower the resistance of the conductive layer, it is preferable that the volume content of the metal oxide particles in the conductive layer is high, but the strength of the layer is not increased. It is preferable to include a binder of at least about 5% in order to sufficiently hold it, and the volume content of the conductive particles is 5 to 5.
A range of 95% is preferred.

The conductive layer containing the reaction product of the water-soluble conductive polymer and the crosslinking agent used in the present invention will be described.

In the present invention, examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from a sulfo group, a sulfate ester group, a quaternary ammonium salt, a tertiary ammonium salt and a carboxyl group. The unit containing a conductive group is preferably 5 mol% or more, more preferably 20 mol% or more, per one molecule of the polymer. One or more conductive groups may be mixed.

The water-soluble conductive polymer may contain a hydroxyl group, amino group, epoxy group, aziridine group, active methylene group, sulfinic acid group, aldehyde group, vinyl sulfone group and the like.

The molecular weight of the polymer is 3000 to 10000.
It is 0, preferably 3500 to 50000.

Examples of the compound of the water-soluble conductive polymer used in the present invention are shown below, but the invention is not limited thereto.

[0052]

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In the above P-1 to P-4, Mn represents a number average molecular weight and is a value measured by GPC in terms of polyethylene glycol.

In the present invention, the water-soluble conductive polymer layer may contain hydrophobic polymer particles. The hydrophobic polymer particles are composed of so-called latex which is substantially insoluble in water. This hydrophobic polymer is obtained by polymerizing monomers selected from any combination of styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile and the like. Especially styrene derivatives, alkyl acrylates,
It is preferable that the content of the alkyl methacrylate is at least 30 mol%. In particular, 50 mol% or more is preferable.

To make the hydrophobic polymer into a latex, there are two methods: emulsion polymerization, dissolution of a solid polymer in a low boiling point solvent, fine dispersion, and evaporation of the solvent. Emulsion polymerization is preferable in that a uniform product can be obtained.

The hydrophobic polymer has a molecular weight of 3000 or more, and there is almost no difference in transparency depending on the molecular weight.

Specific examples of the hydrophobic polymer will be given.

[0058]

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[0059]

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In the present invention, a polyfunctional aziridine or epoxy compound is preferable as the crosslinking agent used together with the water-soluble conductive polymer. 2 as an aziridine compound
It is preferably functional or trifunctional and has a molecular weight of 700 or less.

Specific examples of preferably used aziridine crosslinking agents are shown below.

[0062]

[Chemical 6]

The epoxy compound preferably contains a hydroxyl group or an ether bond. Particularly, those having an epoxy equivalent of 100 to 300 are preferable. Specific examples of the epoxy compound preferably used include HE-1 to HE-9 mentioned above as preferable specific examples of the epoxy hardener used for curing the hydrophilic colloid layer.

[0064] In the present invention, the coating amount of the water-soluble electroconductive polymer is 100-2000 mg / m ^2, preferably 200~1500mg / m ^2. The hydrophobic latex added to the water-soluble conductive polymer is 0 to 60% by weight, preferably 10 to 30% by weight.

The crosslinking agent added is 5 to 80% by weight, preferably 10 to 50% by weight, based on the water-soluble polymer.

The π-electron conductive polymer used in the present invention is a conjugated system in which a double bond or a triple bond connecting a carbon atom and a carbon atom or a hetero atom is alternately long and continuous with a single bond as a molecular skeleton. Is a conjugated polymer.

These conjugated polymers include 1) aliphatic conjugated systems: polymers in which carbon-carbon conjugated systems such as polyacetylene are alternately long, and 2) aromatic conjugated systems:
Polymers with well-developed conjugation of aromatic hydrocarbons such as poly (paraphenylene), 3) Heterocyclic conjugated systems:
Polymers in which a heterocyclic compound such as polypyrrole or polythiophene is bound to develop a conjugated system, 4) Heteroatom-containing conjugated systems: Polymers in which an aliphatic or aromatic conjugated system such as polyaniline is bound to a heteroatom, 5) Mixtures Type conjugate system:
A conjugated polymer having a structure in which constituent units of the above conjugated system such as poly (phenylene vinylene) are alternately bonded, 6) double-chain conjugated system: a conjugated system having a plurality of conjugated chains in a molecule, which is an aromatic conjugated system Having a structure close to that of the above, 7) Metal phthalocyanines: Metal phthalocyanines or polymers in which these molecules are linked by heteroatoms or conjugated systems, 8)
Conductive complex: a polymer obtained by graft-copolymerizing the conjugated polymer chain with a saturated polymer, a complex obtained by polymerizing the conjugated polymer in a saturated polymer, and the like. It can be applied to the present invention as a conductive polymer.

When the above-mentioned π-electron conductive polymer is shown below as a polymer group, 1) is polyacetylene, poly (1,6-heptadiene), etc., and 2) is
Poly-p-phenylene, polynaphthalene, polyanthracene, etc. 3) include polypyrrole and its derivatives, polyfuran and its derivatives, polythiophene and its derivatives,
As polyisothionaphthene and its derivatives, polyselenophene and its derivatives, etc., 4), polyaniline and its derivatives, poly (p-phenylene sulfide) and its derivatives, poly (p-phenylene oxide) and its derivatives, poly (P-phenylene selenide) and its derivatives, and in aliphatic systems, poly (vinylene sulfide), poly (vinylene oxide), poly (vinylene selenide), etc., 5) include poly (p-phenylene vinylene) and its derivatives , Poly (pyrrole vinylene) and its derivatives, poly (thiophenvinylene) and its derivatives, poly (furan vinylene) and its derivatives, poly (2,2'-thienylpyrrole) and its derivatives, etc., 6) Naphthalene, 7)
As metal phthalocyanine, and as 8) 3)
Polythiophene (including derivative), polypyrrole (including derivative), 4) polyaniline (including derivative), and 5) poly (p-phenylene vinylene) (including its derivative), poly (thiophene vinylene) ) (Including its derivative) and the like in a side chain through a connecting group, a π-electron conductive polymer composite of a polymer and the like can be mentioned.

Among the above, the heterocyclic conjugated system of 3), 4)
The heteroatom-containing conjugated system of 5), the mixed conjugated system of 6), 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 used in the present invention. .

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

[0071]

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The description of the substituents in the above formula is described in Japanese Patent Application No. 6-30.
No. 2273, paragraphs 0016 to 0035, and specific compound examples are described in paragraphs 0058 to 0068 of the same application.
It is described as SP (I) -1 to ASP (V) -7.

In the present invention, the content of the π-electron conductive polymer in the conductive layer is preferably 0.5 to 50% by weight, and particularly 1 to 20% by weight in the composition in order to enhance the conductivity. Is preferred.

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

The method of polymerizing the above-mentioned polymers is described in detail in "Conductive Polymers" edited by Naoya Ogata, pp. 57-93, and more specifically, JP-A-2-255770.
No. 2-252726, J. Chem. Soc. C
hem. Commun. , 1983, p. 854, J.
Polym. Sci. Polym. Lett. ed. ,
18, p. 9 (1980), J. Am. Chem. Soc. C
hem. Commun. 1986, 1348, Po
27, 455 (1986), Synt
hitic Metals, 26, 383 (198)
8), Polymer Commun. , Volume 28, 22
Page 9 (1987) and the like, and can be synthesized by these.

As the dopant of the π-electron conductive polymer, halogen molecules (Cl ₂ , Br ₂ , I ₂ , ICl, I
Cl ₃ , IBr, IF, etc.), Lewis acid (PF ₅ , AsF ₅ ,
SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ , SO _3, etc., protic acid (HF, HCl, HNO ₃ , H ₂ SO ₄ , HCl)
O ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, various organic acids, amino acids, etc., transition metal compounds (FeCl ₃ , F
eOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , Nb
F ₅ , NbCl ₅ , TaCl ₅ , MoF ₅ , MoCl ₅ , W
F ₆ , WCl ₆ , LnCl ₃ (Ln = La, Ce, Pr,
Lanthanoids such as Nd and Sm), electrolyte anions (Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ ,
SbF ₆ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , CH ₃
SO ₃ ⁻ , CH ₃ C ₆ H ₅ SO ₃ ^−, etc., polymer electrolyte anion (polyvinyl sulfate, polystyrene sulfonic acid, poly (p-vinylbenzyl sulfonic acid), polyacrylic acid,
Polyethylene sulphonic acid, polyvinyl sulphonic acid, polyphosphoric acid, polyaspartic acid, etc.) and others, O ₂ , X
eOF ₄ , (NO ₂ ⁺ ) (SbF ₆ ), (NO ₂ ⁺ ) (SbC
^{_{L 6 -), (NO 2}} +) (BF 4 -), FSO 2 OOSO 2 F,
_{AgClO 4, H 2 IrCl 6,} La (NO 3) 3 · 6H 2 O
However, the present invention is not limited to these. Among these, I ₂ , Br ₂ , HCl, H ₂ SO ₄ , AsF
₅ , SbF ₅ , KBF ₄ , LiBF ₄ , (C ₂ H ₅ ) ₄ NB
F ₄ , FeCl ₃ , LiClO ₄ , CF ₃ SO ₃ Li, CF _{3
SO 3 Na, CF 3 SO 3} H, LiBr, p- toluenesulfonic acid, and polystyrene sulfonic acid are preferably used.

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

As a method of doping, for example, doping can be performed by allowing a dopant to exist in the polymerization field of the π-electron type conductive polymer. Also, a dopant may be added when preparing the coating liquid for the conductive layer,
In-situ doping is preferred. 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 doped dopant is preferably present in an amount of 1 mol% or more per repeating unit of the π-electron conductive polymer, and when it is 10 mol% or more, a more stable conductivity level can be obtained. preferable.

Typical examples of the combination of the π-electron conductive polymer and the dopant used in the present invention are shown below.

[0081]

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[0082]

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[0083]

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The polymer ionic solid electrolyte to be contained in the conductive layer is not particularly limited, but preferably the polymer shown below (hereinafter referred to as "polymer X") and the metal salt shown below (hereinafter referred to as "polymer X"). “Metal salt Y”), which is a complex formed by polymer X and metal salt Y
Is characterized by forming a polymer ionic solid electrolyte. Therefore, with the polymer X and the metal salt Y, the photographic constituent layer of the color light-sensitive material can be coated without using the conventional method of using a binder such as dispersing in a hydrophilic colloid or latex.

As the polymer X, polyethylene oxide units, polypropylene oxide units, polymethyl vinyl ether units, polystyrene sulfide units, poly-
Examples of the polymer include monomers having a β-caprolactone unit, a polyethylene succinate unit, a polyethyleneimine unit, and the like, and a polymer having a polyethylene oxide unit or a polyethyleneimine unit is particularly preferable.

Examples of the polymer having a polyethylene oxide unit include, but are not limited to, the followings.

[0087]

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[0088]

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[0089]

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[0090]

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These polymers are known, and the production method is described in US Pat. No. 4,542,095, JP-A-61-161.
41143, 61-47713, 60-199.
047, 60-179448 and the like. In addition, some of the Pluronic P123 (BAS
F company), Tetronics T1304 (BASF company),
Surfynol 465 (manufactured by Air Products), Q
Commercially available under the names of 4-3667 (manufactured by Dow Corning), Monflor 51 (manufactured by ICI), PS071, PS073 (manufactured by Petrarch Systems), Silwet L-7605 (manufactured by Union Carbide) and the like.

Furthermore, among the above-mentioned polymers having polyethylene oxide units, P-9 to P-11 and P-13
Vinyl polymers such as may be copolymerized with other copolymerizable vinyl monomers (A).

Other vinyl monomers (A) are not particularly limited, but include, for example, alkyl acrylate, alkyl methacrylate, monoalkyl itaconate, dialkyl itaconate, acrylonitrile, acrylamide,
Examples thereof include vinyl acetate, styrene, divinylbenzene, glycidyl acrylate, monoalkyl malate, dialkyl malate, monoalkyl fumarate, dialkyl fumarate, acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid. And the vinyl monomer (A) to be copolymerized may be two or more kinds.

Specific examples of the vinyl monomer (A) are shown below.
In addition, the molar ratio of the ethylene oxide monomer (x) and the vinyl monomer (A) (y) and the degree of polymerization (n) are shown.
It is not limited to these.

[0095]

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[0096]

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Further, examples of the polymer having a polyethyleneimine unit include, but are not limited to, the followings.

[0098]

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R: Alkyl group having 1 to 5 carbon atoms The above polymers are known, and the production method is disclosed in JP-A-61-4.
No. 2520, Macromolecule 18, Vol. 825 (1
985) and the like.

As the molecular weight of the polymer X, any number average molecular weight in terms of polystyrene by GPC of 1,000 to 500,000 can be preferably used, and particularly 100
0 to 100,000 is preferable.

Examples of the metal salt Y include sodium iodide, sodium bromide, sodium chloride, sodium thiocyanate, potassium thiocyanate, sodium perchlorate, lithium perchlorate, sodium tetrafluoride, rubidium thiocyanate, and iodide. Examples thereof include alkali metal salts such as rubidium, and mercury chloride. Among them, silver hydrohalide, thiocyanate, nitric acid, sulfuric acid, phosphoric acid, halogen oxyacid, perhalogen oxyacid, tetrahalogen boric acid or hexahalogen phosphoric acid Alkali metal salts are most preferred.

The addition amount of the metal salt Y is 0.01 to 1.0 equivalent, preferably 0.02, per one monomer such as ethylene oxide unit or ethyleneimine unit in the polymer X.
~ 0.5 equivalent. That is, if the amount is less than 0.01 equivalent, it is difficult to obtain high conductivity, complex formation with the polymer X is insufficient, and if it exceeds 1 equivalent, it is difficult to uniformly dissolve the polymer.

In order to add the metal salt Y to the polymer X and dissolve it, the metal salt Y can be added directly to the polymer X and, if necessary, dissolved by stirring, but it is also possible to use methanol, ethanol or methoxyethylene. Glycol, dimethylformamide, dimethylsulfoxide,
A method in which a metal salt is dissolved in a polar solvent such as water and then a polymer is added to form a uniform solution is preferable.

The conductive layer of the present invention is formed by applying and drying the uniform solution thus prepared.

The coating amount of the polymer X is 10 to 2000 mg.
/ M < ² >, especially 50-1000 mg / m < ² > is preferable.

The present invention can be applied to monochrome photographic light-sensitive materials such as X-ray films and printing films, and color photographic light-sensitive materials such as color negative films and color reversal films.

The case where the present invention is applied to the back layer of a color negative film will be described in detail.

When the present invention is applied to a color light-sensitive material, the silver halide emulsions of the red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers can be those described in RD308119. The places to be described are shown below.

[Item] [Page of RD308119] Iodine composition 993 IA item Production method 993 I-A item and 994 E item Crystal habit (normal crystal) 993 IA item Crystal habit (twin crystal) 993 IA Item Epitaxial 993 I-A Item Halogen composition (uniform) 993 I-B Item Halogen composition (non-uniform) 993 I-B Item Halogen conversion 994 I-C Item Halogen substitution 994 I-C Metal content 994 I-D Item Monodisperse 995 I-F Item Solvent addition 995 I-F Item Latent image forming position (surface) 995 I-G item Latent image forming position (internal) 995 I-G Item Sensitive material (negative) 995 I-H item Applied Sensitive Material (Positive) 995 I-H Item Mixed with Emulsion 995 I-J Item Desalting Item 995-A Each of the red, green and blue sensitivities of the color light-sensitive material of the present invention. The silver halide emulsion of the silver halide emulsion layer can be a silver halide emulsion spectrally sensitized with a supersaturated solution of a sensitizing dye. Here, the supersaturated solution of the sensitizing dye refers to a solution in which the sensitizing dye exists in water or an organic solvent in excess of its solubility. That is, the supersaturated liquid may be a supersaturated solution, an emulsion dispersion liquid, or a solid fine particle dispersion liquid. Among these, a solid fine particle dispersion liquid in water or an organic solvent is preferable, and a solid sensitizing dye dispersion liquid in water is particularly preferable.

The solid sensitizing dye dispersion in water is a dispersion of the spectral sensitizing dye in an aqueous system in an amount exceeding the solubility in water at 27 ° C. and mechanically dispersed in solid fine particles of 1 μm or less. . Preferred is a “solid dispersion in water of a substantially water-insoluble photographic spectral sensitizing dye for organic solvent-free”, which has a solubility at 27 ° C. in an aqueous system in which an organic solvent and / or a surfactant is not present. 1 x 10 ^-4 to 4 x
10 ⁻² mol / liter, preferably 2 × 10 ⁻⁴ to 4 × 1
A spectral sensitizing dye of 0 ^-2 mol / liter was added in an amount exceeding the solubility and mechanically dispersed in solid fine particles of 1 µm or less.

A technique for mechanically dispersing an organic dye in an aqueous medium is known from JP-A-3-288842. However, this method is for making an organic dye resistant to diffusion in a photographic light-sensitive material, and is merely a dispersion addition method.

On the other hand, the above-mentioned spectral sensitization method is intended to uniformly and effectively adsorb the photographic spectral sensitizing dye on the surface of the silver halide grain, and it is merely added in a dispersed manner. Technology is different from the purpose and effect.

The above-mentioned organic solvent means a solvent containing carbon atoms which is liquid at room temperature.

Conventionally, a water-miscible organic solvent has been used as a solvent for sensitizing dyes. Alcohols,
Examples thereof include ketones, nitriles, alkoxy alcohols and the like. Specific examples include methanol, ethanol, propyl alcohol, i-propyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like.

The above-mentioned solid sensitizing dye dispersion in water does not substantially contain these organic solvents. The surfactants include anionic, cationic, nonionic and betaine type surfactants.

Conventionally, these surfactants have been used as dispersants for sensitizing dyes, but the dispersion is substantially free of these surfactants. Here, the aqueous system in which an organic solvent and / or a surfactant is substantially absent is water containing impurities at a level not adversely affecting the silver halide photographic emulsion, and more preferably ion-exchanged water. .

The solubility of the spectral sensitizing dye in water in the solid type sensitizing dye dispersion in water is 2 × 10 ⁻⁴ to 4 × 1.
It is 0 ^-2 mol / liter, more preferably 1 x 10
⁻³ to 4 × 10 ⁻² mol / liter. That is, if the solubility is lower than this range, the dispersed particle size is very large, and
Because of non-uniformity, the dispersion precipitates after the dispersion is completed, or when the dispersion is added to the silver halide emulsion, the process of adsorbing the dye on the silver halide is hindered. On the other hand, if the solubility is higher than this range, the viscosity of the dispersion is increased more than necessary, air bubbles are entrapped, which hinders dispersion, and dispersion becomes impossible at higher solubility.

The solubility of the spectral sensitizing dye in water was measured by the following method.

Ion exchange water was added to a 50 ml Erlenmeyer flask.
Add 0 ml, add an amount of dye that is not completely dissolved visually,
The mixture was kept at 27 ° C. in a thermostat and stirred with a magnetic stirrer for 10 minutes. The suspension was treated with Toyo Co., Ltd. The mixture was filtered through 2 and the filtrate was filtered through a disposable filter of Tosoh Corp., the filtrate was diluted appropriately, and the absorbance was measured with a spectrophotometer [U-3410 manufactured by Hitachi, Ltd.].

As a result, Lambert-Beer's law D =
The solubility (mol / liter) was determined from εlc (D: absorbance, ε: spectral absorption coefficient, l: cell length for absorbance measurement, c: concentration (mol / liter)).

The term "sensitizing dye" as used herein means a substance which causes electron transfer to silver halide when adsorbed to silver halide and photoexcited, and does not include organic dyes.

The above sensitizing dye has a solubility in water of 2 ×.
Any dye may be used within the range of 10 ⁻⁴ to 4 × 10 ⁻² mol / liter, and a cyanine dye is preferable. More preferably, it is a cyanine dye having a hydrophilic group (for example, a sulfo group or a carboxyl group).

Mechanically grinding the sensitizing dye in an aqueous solvent,
Various dispersers are effectively used for dispersion. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser, or the like is used. In the present invention, a high speed stirrer is preferred.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on the vertical shaft or a multi-axis dissolver having a plurality of vertical shafts.

Further, in addition to the dissolver alone, a high speed stirring type disperser having an anchor blade is more preferable. As a specific working example, after putting water in a tank whose temperature can be adjusted, a certain amount of powder of the spectral sensitizing dye is put, and the mixture is stirred for a certain period of time under temperature control with a high-speed stirrer,
Crush and disperse.

The pH and temperature at which the sensitizing dye is mechanically dispersed are not particularly limited, but the desired particle size cannot be reached even after long-term dispersion at low temperature, and reaggregation or decomposition may occur at high temperature. As a result, there are problems that desired photographic performance cannot be obtained and that the viscosity of the solution system decreases when the temperature is raised, so that the efficiency of pulverization and dispersion of solids is greatly reduced. Therefore, the dispersion temperature is more preferably 15 to 50 ° C.

Further, the stirring rotation number during dispersion requires a long time to obtain a desired particle size at a low rotation number, and entrains bubbles at a high rotation number to lower the dispersion efficiency.
It is preferable to disperse at 6000 rpm.

When the solid fine particles of the sensitizing dye dispersed by the above method are 1 μm or less, it means that the particle size according to the volume average diameter of spheres is 1 μm or less, and it can be measured by a general method.

The above-mentioned "dispersion" means a suspension of the sensitizing dye, and preferably the weight ratio of the spectral sensitizing dye in the suspension is 0.2 to 5.0%. Is used.

The dispersion of the sensitizing dye may be added directly to the silver halide emulsion or may be added after appropriately diluting it. Water is used as a diluting solution at this time.

The silver halide emulsion according to the present invention can be used after physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD
17643, RD18716 and RD308119. The types and locations of the compounds described in these three RDs are described below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, Item J 23-24 648-9 Supersensitizer 996 IV-AE, Item J 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Color turbidity inhibitor 1002 Item VII-I 25 650 Dye image stabilizer 1001 Item VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIIIC, XIII-C Item 25-26 Light absorber 1003 VIII 25-26 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 Matte agent 1007 XVI developer (included in light-sensitive material) 1011 XXB Item The color light-sensitive material of the present invention contains U.S. Pat. No. 4,4,419 in order to prevent deterioration of photographic performance due to formaldehyde gas.
It is preferable to add to the light-sensitive material a color compound that can be fixed by reacting with formaldehyde described in JP-A-11-987 and JP-A-4,435,503.

The additives used in the color light-sensitive material of the present invention can be added by the dispersion method described in RD308119, XIV.

As the support of the color light-sensitive material of the present invention, the above-mentioned RD17643 page 28, RD18716 6 is used.
The supports described on pages 47-8 and RD308119, XIX can be used.

The support of the light-sensitive material of the present invention is preferably a support made of polyester, particularly polyethylene terephthalate or polyethylene naphthalate.

The light-sensitive material of the present invention includes the above-mentioned RD3081.
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19VII-K can be provided.

The light-sensitive material of the present invention is the same as the above-mentioned RD30811.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, and color positive films.

The light-sensitive material of the present invention is the above-mentioned RD17643.
Pages 28 to 29, RD18716 page 615 and RD30
The development can be carried out by the usual method described in XIX of No. 8119.

[0140]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 << Preparation of Seed Crystal Emulsion-1 >> A seed crystal emulsion was prepared as follows.

JP-B-58-58288 and 58-58
An aqueous solution of silver nitrate (1.161 mol) was added to the following solution A1 prepared at 35 ° C. using the mixing stirrer shown in No. 289.
And a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) at the same time while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. Was added over 2 minutes to form nuclei. Subsequently, the liquid temperature was raised to 60 ° C. over 60 minutes, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution, and then an aqueous silver nitrate solution (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% potassium iodide) was added over 42 minutes by the simultaneous mixing method while maintaining the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing with water were immediately performed using a usual flocculation method.

The resulting seed crystal emulsion-1 had an average spherical equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and 90% or more of the total projected area of silver halide grains had a maximum side ratio of 1.
The emulsion consisted of 0 to 2.0 hexagonal tabular grains.

[Solution A1] Ocein gelatin 24.2 g Potassium bromide 10.8 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml << iodination Preparation of silver fine grain emulsion SMC-1 >> 5 l of 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide
While vigorously stirring, 7.01 mol of silver nitrate aqueous solution and 7.06 mol of potassium iodide aqueous solution, 2 l each, were added over 10 minutes. During this time, the pH is 2.0 using nitric acid.
And the temperature was controlled at 40 ° C. After the particles were prepared, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is called SMC-1.

<< Preparation of Emulsion Em-1 >> 4.5 ml containing 0.178 mol of seed crystal emulsion-1 and 0.5 ml of 10% ethanol solution of polyisopropylene-polyethyleneoxy-disuccinate sodium salt. 700 ml of a weight% inert gelatin aqueous solution was kept at 75 ° C. and pAg was adjusted to 8.
3, after adjusting the pH to 5.0, particles were formed by the following procedure by the simultaneous mixing method with vigorous stirring.

1) 2.121 mol of silver nitrate aqueous solution and 0.
174 mol of the SMC-1 and potassium bromide aqueous solution were added while keeping pAg at 8.3 and pH at 5.0. (Formation of Host Particles) 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg was adjusted to 9.6. Then, 0.071 mol of SMC-1 was added and aging was performed for 2 minutes. (Introduction of Dislocation Line) 3) 0.959 mol of silver nitrate aqueous solution, 0.030 mol of SMC-1 and potassium bromide aqueous solution were added while keeping pAg at 9.6 and pH at 5.0. (Shelling of host particles) Each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles from progressing through the formation of particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The resulting emulsion Em-1 had a grain size (cubic 1 side length of the same volume) of 0.65 μm and an average aspect ratio of 4.1.
The emulsion consisted of tabular grains having the halogen composition shown in Table 1 above. Observation of this emulsion with an electron microscope 8
Five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 0% or more (the number) of grains.

<< Preparation of Sensitizing Dye Solid Dispersion Liquid SD-A >> 333 mg of each of the sensitizing dyes SD-9, SD-10, and SD-11 described below were weighed, and 50 m of water preliminarily adjusted to 27.degree.
After adding 1, add 350 with a high-speed stirrer (dissolver).
By stirring at 0 rpm for 30 to 120 minutes, a sensitizing dye solid dispersion liquid (SD-A) having an average particle diameter of 0.38 μm was obtained.

<< Preparation of Sensitizing Dye Methanol Solution SD-B >> The sensitizing dyes SD-9, SD-10, SD-11 described later.
Was weighed 200 mg each, and 100 ml of methanol whose temperature was adjusted to 27 ° C. was added in advance to obtain a sensitizing dye methanol solution (SD-B) dissolved at 27 ° C.

Sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to the emulsion Em-1 using the sensitizing dye solid dispersion SD-A and the sensitizing dye solution SD-B, and the fog was formed according to a conventional method. Chemical sensitization was performed to optimize the sensitivity relationship.

<< Preparation of Support A Having Conductive Layer >> A polyethylene terephthalate support having a thickness of 180 μm was subjected to corona discharge treatment on both surfaces thereof, and then the first subbing composition shown below was used.
The layers were applied and dried at 100 ° C.

Emulsion layer side subbing first layer Polyco (butyl acrylate-styrene-ter-butyl acrylate-hydroxyethyl methacrylate) latex average particle size 0.09 μm 350 mg / m ² anionic surfactant SU-5 4 mg / m ² Crosslinking agent HA-2 15 mg / m ² Backside layer-side undercoating first layer Polyco (styrene-butyl acrylate-glycidyl methacrylate) Latex average particle size 0.07 μm 800 mg / m ² Anionic surfactant SU-5 10 mg / m ² Crosslinking agent HA-2 10 mg / m ² Further, a subbing second layer having the following composition was applied on the subbing first layer after corona discharge treatment, and dried at 100 ° C.

Emulsion layer side subbing second layer Polyco (maleic acid half ester of styrene-fluorinated alcohol) 10 mg / m ² anionic surfactant SU-6 2 mg / m ² crosslinking agent CH ₃ SO _3- (CH ₂ ) ₃ -SO ₃ CH ₃ 1 mg / m ² Silica fine particles Average particle size 3 μm 3 mg / m ² Back layer side undercoating second layer (conductive layer) Polyco (sodium styrenesulfonate-maleic acid) Water-soluble conductive polymer P -3 Latex of 600 mg / m ² hydrophobic polymer L-5 Average particle size 0.08 μm 300 mg / m ² Epoxy hardener (crosslinking agent) HE-5 100 mg / m ² After coating and drying the second undercoat layer, A heat treatment was performed at 140 ° C. for 2 minutes to prepare a support A.

Further, as the backside second undercoating layer, an undercoated support D was prepared in which an emulsion layer side undercoating second layer was provided in place of the backside layer side undercoating second layer.

Further, a subbing-completed support B provided with a backing layer-side subbing second layer (types and amounts of metal oxide fine particles are shown in Table 1) below instead of the backing layer-side subbing second layer. ,
And an undercoated support C having the following backside second undercoating second layer (type and amount of π-electron conductive polymer shown in Table 1) instead of the above backside undercoating second layer. did.

Second layer on the back surface layer side (containing fine metal oxide particles) SnO ₂ particles (SnO ₂ / Sb = 85/15; volume resistance 10 ⁷ Ωcm, average particle size 0.15 μm) 0.6 g / m ² Gelatin 0.3 g / m ² Hardener (H-3) CH ₂ = CHSO ₂ CH ₂ CH (OH) CH ₂ SO ₂ CH = CH ₂ 0.02 g / m ² Backside _second subbing layer (π Electronic conductive polymer included) Butyl acrylate-styrene-glycidyl acrylate (40:20:40 wt%) copolymer latex (average particle size 0.07 μm, solid content 30%) 0.81 g / m ² anionic surfactant (SU-1) 0.006g / m 2 gelatin 0.05 g / m ² [pi electron conductive polymer (ASP (I) -1, those that have been ground to an average particle size of 0.15μm) 0.3g / m ² hardness Membrane agent (H-1) aqueous solution (solid content 0.5%) Each layer of the following composition was sequentially coated on the undercoated support of 0.001 g / m ² or more from the support side by a slide hopper to prepare a color light-sensitive material sample.

The coating amount of silver halide and colloidal silver is the amount expressed in g / m ² in terms of metallic silver.
Also, for couplers, additives and gelatin, g / m ²
The amount added in units is also shown for the sensitizing dye in terms of moles per mole of silver halide in the same layer.

Composition of Photographic Image Forming Layer First Layer: Antihalation Layer Black Colloidal Silver 0.18 UV Absorber (UV-1) 0.30 High Boiling Solvent (Oil-1) 0.37 Gelatin 1.59 Second Layer: Intermediate layer Gelatin 1.27 Third layer: Low sensitivity red-sensitive layer Silver iodobromide emulsion A 0.63 Sensitizing dye (SD-1) 1.7 × 10 ⁻⁴ Sensitizing dye (SD-2) 1 0.5 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.5 × 10 ⁻⁴ Sensitizing dye (SD-4) 1.3 × 10 ⁻⁵ Cyan coupler (C-1) 0.71 Colored cyan coupler ( CC-1) 0.09 DIR compound (D-1) 0.005 High-boiling point solvent (Oil-1) 0.63 Gelatin 2.05 Fourth layer: middle-sensitive red-sensitive layer Silver iodobromide emulsion B 0.71 sensitizing dye (SD-2) 2.5 × 10 -4 sensitizing dye (SD-3) 1.4 × 10 -5 sensitizing dye (S ^-4) 2.2 × 10 -4 Cyan coupler (C-1) 0.27 Colored cyan coupler (CC-1) 0.04 DIR compound (D-2) 0.01 High boiling solvent (Oil-1) 0 .32 Gelatin 0.83 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion C 1.52 Sensitizing dye (SD-2) 2.1 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ^-5 Sensitizing dye (SD-4) 1.8 × 10 ^-4 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.009 High boiling point solvent (Oil-1) 0. 17 Gelatin 1.04 Sixth layer: Intermediate layer Gelatin 1.00 Seventh layer: Low-sensitivity green sensitive layer Silver iodobromide emulsion A 0.76 Sensitizing dye (SD-1) 6.5 × 10 ⁻⁴ Sensitizing dye (SD-5) 7.2 × 10 -5 magenta coupler (M-1) 0.10 magenta coupler (M-2) .25 Colored magenta coupler (CM-1) 0.11 DIR compound (D-1) 0.004 DIR compound (D-3) 0.013 High boiling point solvent (Oil-2) 0.49 Gelatin 1.10 Eighth Layer: Medium sensitivity green sensitive layer Silver iodobromide emulsion B 0.55 Sensitizing dye (SD-1) 5.2 × 10 ⁻⁴ Sensitizing dye (SD-5) 5.8 × 10 ⁻⁵ Magenta coupler (M -1) 0.07 Magenta coupler (M-2) 0.17 Colored magenta coupler (CM-1) 0.08 DIR compound (D-1) 0.001 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.33 Gelatin 0.78 9th layer: High-sensitivity green-sensitive layer Em-1 0.82 SD-A 0.0033 Sensitizing dye (SD-11) 1.4 × 10 ^-4 Sensitizing dye Dye (SD-5) 1.5 × 10 ⁻⁴ Sensitizing Dye (SD-9) ) 1.4 × 10 ⁻⁴ Magenta coupler (M-2) 0.10 Magenta coupler (M-3) 0.03 Colored magenta coupler (CM-2) 0.001 DIR compound (D-1) 0.001 DIR Compound (D-3) 0.004 High boiling point solvent (Oil-2) 0.31 Gelatin 0.91 10th layer: Intermediate layer Gelatin 0.50 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC -1) 0.08 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 12th layer: Intermediate layer Gelatin 0.50 13th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion A 0.16 Iodine Silver bromide emulsion D 0.16 Sensitizing dye (SD-6) 1.7 × 10 ^-4 Sensitizing dye (SD-7) 4.0 × 10 ^-4 Yellow coupler (Y-1) 0.24 Yellow coupler (Y-2) 0.66 High boiling point The solvent (Oil-2) 0.18 Gelatin 1.19 14th layer: middle sensitivity blue-sensitive layer Silver iodobromide emulsion B 0.46 Sensitizing dye (SD-6) 1.3 × 10 -4 Sensitizing dye ( SD-7) 3.0 × 10 ⁻⁴ Yellow coupler (Y-1) 0.07 Yellow coupler (Y-2) 0.20 High boiling point solvent (Oil-2) 0.05 Gelatin 0.84 Fifteenth layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion E 0.41 Sensitizing dye (SD-6) 0.9 × 10 ⁻⁴ Sensitizing dye (SD-8) 2.0 × 10 ⁻⁴ Yellow coupler (Y-1) ) 0.06 Yellow coupler (Y-2) 0.18 High boiling point solvent (Oil-2) 0.05 Gelatin 0.97 16th layer: 1st protective layer Silver iodobromide (average particle size 0.04 μm, iodine Silver halide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.030 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.015 High boiling point solvent (Oil-2) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 1.44 17th layer: 2nd protective layer Alkali-soluble matting agent (PM-1, average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding Agent (WAX-1) 0.04 Gelatin 0.55 SU-3, SU-4 0.006 Back layer composition Back layer first layer Gelatin 7.0 Polyacrylic acid of the present invention (10 wt%, at pH 6) Adjusted and added) Listed in Table 1 Epoxy hardener of the present invention Listed in Table 1 Back layer Second layer Gelatin 1 Anionic surfactant (Su-1) 0.006 Polymethylmethacrylate having an average particle diameter of 3 μm 0 ． 04 It is to be noted that the above-mentioned light-sensitive material further comprises compounds SU-1 and SU-
2, viscosity modifier, hardener H-1, H-2, stabilizer ST-
1, antifoggants AF-1 and AF-2 (weight average molecular weights of 10,000 and 1,100,000), dye A
I-1, AI-2, AI-3, FS-1, FS-2 and compound DI-1 were added appropriately.

The comparative samples are hardeners H-1 and H-2.
Was adjusted so that the swelling degree was the same as that of the present invention.

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

Emulsion name Average AgI Average particle size Crystal habit Diameter / thickness ratio Content (mol%) (μm) Emulsion A 8.0 0.42 Normal crystal 1 Emulsion B 8.0 0.55 Normal crystal 1 Emulsion C 8 0.0 0.75 Twin tabular emulsion 2 Emulsion D 2.0 0.32 Normal crystal 1 Emulsion E 8.0 0.90 Twin tabular emulsion 2 Emulsions A and D contain 1 × 10 ⁻⁷ mol / lmol Ag of iridium ing.

The structures of the compounds added to the respective layers of the above light-sensitive material are shown below.

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[Chemical 21]

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The above color light-sensitive material samples were wedge-exposed with white light and subjected to a developing treatment described later according to a conventional method, and the surface specific resistance after the developing treatment was measured. In addition, the film strength in the developing solution was measured separately.

<< Surface Resistivity >> The coated sample was treated at 23 ° C.
The measurement was performed using a teraohm meter (Kawaguchi Electric Co., Ltd .: Model VE-30) in an atmosphere of 55% RH.

<Film Strength> In particular, since easiness of scratches in the developing solution becomes a problem, evaluation was made by the following swelling film strength evaluation method.

Swelling film strength evaluation method The coated sample was cut into a piece having a width of 3.5 cm and a length of 14 cm, immersed in a color developing treatment solution at 38 ° C. for 3 minutes, and then a sapphire needle having a diameter of 0.5 mm was formed into a film. 5mm /
The load on the needle was continuously changed while moving at a speed of sec, and the load (g) when the film was broken was expressed.

<< Development processing >> Processing step Processing time Processing temperature (° C.) Color development 3 minutes 15 seconds 38 Bleach 45 seconds 38 Settling 1 minute 45 seconds 38 Stabilization 90 seconds 38 Dry 1 minute 40 to 70 (color development Liquid) Potassium carbonate 30 g Sodium hydrogen carbonate 2.7 g Potassium sulfite 2.8 g Sodium bromide 1.3 g Hydroxylamine sulfate 3.2 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyl ethyl) Aniline sulfate 4.6 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.3 g Water is added to make 1,000 ml, and the pH is adjusted to 10.01 using potassium hydroxide or 20% sulfuric acid.

The composition of the bleaching solution used is as follows.

(Bleaching Solution) 1,3-Diaminopropanetetraacetic acid ferric ammonium 137 g Ethylenediaminetetraacetic acid disodium 2.0 g Ammonium bromide 150 g Glacial acetic acid 40 ml Ammonium nitrate 40 g Water was added to 1,000 ml to prepare ammonia water or ice. PH = 4 with acetic acid. Adjust to 5.

The compositions of the fixer and fixer replenisher used are as follows.

(Fixer) Ammonium thiosulfate 100 g Ammonium thiocyanate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetic acid 1.0 g Water was added to 700 ml, and pH was adjusted using glacial acetic acid and aqueous ammonia. = Adjust to 6.5.

The compositions of the stabilizing solution and stabilizing replenishing solution used are as follows.

(Stabilizing Solution) 1,2-Benzisothiazolin-3-one 0.1 g p-octylphenol / ethylene oxide 10 mol adduct (50% solution) 2.0 ml Hexamethylenetetramine 0.2 g Hexahydro-1,3,3 5-Tris (2-hydroxyethyl) -s-triazine 0.3 g Water was added to make 1,000 ml, and pH was adjusted to 7.0 using potassium hydroxide and 50% sulfuric acid.

The results are shown in Table 1.

[0185]

[Table 1]

As is apparent from Table 1, according to the present invention, the physical properties of the film are excellent while maintaining the conductivity after the development treatment.

Example 2 0.2 (%) of poly (vinyl acetate-maleic anhydride) on both sides
The following backing layer was applied from the support side to one surface of a 100 μm thick cellulose triacetate film support coated with a μ-thick undercoat layer.

<< Backing Layer >> First Layer Gelatin 3.0 g / m ² Dye BC-1 50 mg / m ² Dye BC-2 25 mg / m ² Dye BC-3 50 mg / m ² High boiling point solvent (OIL-1) 0 .6 g / m ² coating aid (Su-2) 20 mg / m ² Polyacrylic acid of the present invention (10 wt%, added after adjusting to pH 6) Described in Table 2 Hardener of the present invention Described in Table 2 Two-layer gelatin 4.0 g / m ² dye BC-1 50 mg / m ² dye BC-2 25 mg / m ² dye BC-3 50 mg / m ² Polyacrylic acid of the present invention (10 wt%, adjusted to pH 6 and added) ) Described in Table 2 Hardener of the present invention Described in Table 2 Third layer Gelatin 1.0 g / m ² Polymethylmethacrylate particles (average particle size 3 μm) 60 mg / m ² Compound (SF-1) 3 mg / m ² Each layer In addition to the above composition, gelatin hardener H-1 H-
2, coating aid Su-1, viscosity modifier and preservative DI-1
Was added.

Then, using the above-mentioned support, a sample which is a multilayer color light-sensitive material composed of each layer having the following composition was prepared. The coating amount of silver halide and colloidal silver is the amount expressed in g / m ² unit in terms of metallic silver, and that of couplers and additives is the amount expressed in g / m ² unit. Dyes are indicated by the number of moles per mole of silver halide in the same layer.

First layer: antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-1) 0.30 High boiling point solvent (Oil-1) 0.37 Gelatin 1.59 Second layer: Intermediate layer Gelatin 1 .27 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.63 Sensitizing dye (SD-1) 1.7 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.5 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.5 × 10 ⁻⁴ Sensitizing dye (SD-4) 1.3 × 10 ⁻⁵ Cyan coupler (C-1) 0.71 Colored cyan coupler (CC-1) 0. 09 DIR compound (D-1) 0.005 High boiling point solvent (Oil-1) 0.65 Gelatin 2.05 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.71 Sensitizing dye (SD- 2) 2.5 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 -5 sensitizing dye (SD-4) 2.2 × 1 ^-4 cyan coupler (C-1) 0.27 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.01 DIR compound (D-2) 0.015 High boiling solvent (Oil-1 ) 0.32 Gelatin 0.83 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion C 1.52 Sensitizing dye (SD-2) 2.1 × 10 ^-4 Sensitizing dye (SD-3) 1 .2 × 10 ^-5 sensitizing dye (SD-4) 1.8 × 10 ^-4 cyan coupler (C-2) 0.13 DIR compound (D-1) 0.006 DIR compound (D-2) High boiling point solvent (Oil-1) 0.17 Gelatin 1.04 Sixth layer: Intermediate layer Gelatin 1.00 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion A 0.76 Sensitizing dye (SD- 1) 1.8 × 10 ^-4 sensitizing dye (SD-5) 1.8 × 10 -4 sensitizing dye (SD-6) 1.8 ^10-4 Magenta coupler (M-1) 0.10 Magenta coupler (M-2) 0.25 Colored magenta coupler (CM-1) 0.11 DIR compound (D-1) 0.004 DIR compound (D-3 ) 0.013 High boiling point solvent (Oil-2) 0.49 Gelatin 1.10 Eighth layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion B 0.55 Sensitizing dye (SD-1) 1.53 × 10 ^-4 Sensitizing dye (SD-5) 1.53 × 10 ^-4 Sensitizing dye (SD-6) 1.53 × 10 ^-4 Magenta coupler (M-1) 0.07 Magenta coupler (M-2) 0 .17 Colored magenta coupler (CM-1) 0.08 DIR compound (D-1) 0.001 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.33 Gelatin 0.78 Ninth Layer: High-sensitivity green-sensitive layer Silver iodobromide emulsion C 0 .82 Sensitizing dye (SD-1) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-5) 1.5 × 10 ⁻⁴ Sensitizing dye (SD-6) 1.4 × 10 ⁻⁴ Magenta coupler ( M-2) 0.10 Magenta coupler (M-3) 0.03 Colored magenta coupler (CM-2) 0.03 DIR compound (D-1) 0.001 DIR compound (D-3) 0.004 High boiling point Solvent (Oil-2) 0.31 Gelatin 0.91 10th layer: Intermediate layer Gelatin 0.50 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.08 High boiling point solvent (Oil) -2) 0.10 gelatin 1.00 12th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.16 Silver iodobromide emulsion D 0.16 Sensitizing dye (SD-7) 1.7 x 10 ^-4 sensitizing dye (SD-8) 4.0 × 10 -4 sensitizing dye (SD-1 ) 3.1 × 10 ^-6 yellow coupler (Y-1) 0.24 Yellow coupler (Y-2) 0.66 High boiling solvent (Oil-2) 0.18 Gelatin 1.19 13th layer: middle sensitivity blue Sensitive layer Silver iodobromide emulsion B 0.46 Sensitizing dye (SD-7) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-8) 3.0 × 10 ⁻⁴ Sensitizing dye (SD-10) 1 .6 × 10 ^-6 Yellow coupler (Y-1) 0.07 Yellow coupler (Y-2) 0.20 DIR compound (D-4) 0.01 High boiling point solvent (Oil-2) 0.05 14th layer : High-sensitivity blue-sensitive layer Silver iodobromide emulsion E 0.41 Sensitizing dye (SD-7) 0.9 × 10 ⁻⁴ Sensitizing dye (SD-9) 2.0 × 10 ⁻⁴ Yellow coupler (Y- 1) 0.06 Yellow coupler (Y-2) 0.18 High boiling point solvent (Oil-2) 0.05 Gelatin 0.97 First 5 layers: First protective layer Silver iodobromide emulsion (average grain size 0.04 μm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.030 UV absorber (UV -3) 0.015 Ultraviolet absorber (UV-4) 0.015 Ultraviolet absorber (UV-5) 0.015 Ultraviolet absorber (UV-6) 0.10 High boiling point solvent (Oil-2) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 1.44 16th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 SU-3, SU-4 0.006 each In addition to the above composition, compounds SU-1, SU-2, viscosity modifier V-1, hard film Agents H-1, H-2, Stabilizer ST-
1, antifoggant AF-1, two kinds of AF-2 having average molecular weights of 10,000 and 1,100,000, compound FS-
1, FS-2, and preservative DI-1 were added appropriately.

The structures of the compounds added to the respective layers of the above light-sensitive material are shown below.

[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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The silver iodobromide emulsion used in the above sample is as follows. The average particle size is shown as a particle size converted into a cube. In addition, each emulsion is sodium thiosulfate, chloroauric acid,
Potassium thiocyanate was added, and chemical sensitization was performed according to a conventional method so that the fog-sensitivity relationship was optimized.

Emulsion name Average AgI Average particle size Crystal habit Diameter / thickness ratio Content (mol%) (μm) Emulsion A 8.0 0.40 Normal crystal 1 Emulsion B 8.0 0.55 Normal crystal 1 Emulsion C 8 0.0 0.70 Normal crystal 1 Emulsion D 2.0 0.30 Normal crystal 1 Emulsion E 8.5 0.85 Normal crystal 1 Emulsions A and D each contain 1 × 10 ⁻⁷ mol / 1 mol Ag of iridium.

Each sample was treated and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0208]

[Table 2]

[0209]

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As is clear from Table 2, according to the present invention, the physical properties of the film are excellent while maintaining the conductivity after the development treatment.

[0211]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which maintains conductivity even after development and does not deteriorate in physical properties.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support,
A silver halide photographic light-sensitive material characterized in that at least one of the hydrophilic colloid layers contains a polyacrylic acid-epoxy crosslinked product. 2. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support,
At least one layer of the hydrophilic colloid layer contains at least one selected from polyacrylic acid and salts thereof, and is hardened with at least one selected from an epoxy hardener and a carboxyl group activated hardener. A silver halide photographic light-sensitive material characterized in that 3. A conductive layer is provided between the hydrophilic colloid layer and the support, wherein the conductive layer is provided.
The silver halide photographic light-sensitive material as described above. 4. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support,
A silver halide photographic light-sensitive material characterized in that at least one of the hydrophilic colloid layers contains at least one selected from polyacrylic acid and salts thereof, and has a conductive layer between it and a support. 5. A silver halide photographic light-sensitive material having, on a support, at least two hydrophilic colloid layers containing at least one selected from polyacrylic acid and salts thereof, wherein the hydrophilic colloid layers are The amount of at least one selected from polyacrylic acid and its salt contained in the hydrophilic colloid layer located in the position close to the support is such that the polyacrylic acid contained in the hydrophilic colloid layer located in the position farther from the support and its A silver halide photographic light-sensitive material characterized by being contained in an amount less than at least one selected from salts.