JPH08339049A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain the silver halide color photographic sensitive material having a hydrophilic colloidal backing layer free from trouble of having scraps mixed at the time of cutting by hardening the backing layer with an epoxy type hardener. CONSTITUTION: The color photographic sensitive material has at least each one of red-, green-, and blue-sensitive silver halide emulsion layers on one side of a support and on the other side the backing layer hardening with the epoxy type hardener having a molecular weight of, preferably, 100-1500 and an epoxy equivalent of, preferably, 100-300. As the binder for forming the backing layer, a hydrophilic colloid, especially, gelatin is preferable. It is preferred that the epoxy hardener is used in the range of 0.001-0.5g/g of the gelatin contained in the backing layer, and 0.005-0.3g is more preferable.

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 color photographic light-sensitive material in which dust is unlikely to be mixed with chips during cutting.

[0002]

2. Description of the Related Art Generally, a silver halide color photographic light-sensitive material (hereinafter abbreviated as "color light-sensitive material") having a backing layer made of a hydrophilic colloid such as gelatin is a large-sized color whose planarity is important. It is used as a photosensitive material. Further, as a support, a polyester film is often used because of its flatness.

By the way, a color light-sensitive material is a coupler,
A lipophilic photographic additive such as an ultraviolet absorber is dispersed in a high boiling point organic solvent such as dioctyl phthalate and is contained in a photographic constituent layer of a color light-sensitive material. The color light-sensitive material is very easily charged due to the influence of these photographic additives, and this tendency is particularly strong in the color light-sensitive material using a polyester film as a support. This electrification causes a failure in which chips are mixed when the film applied in the photosensitive material manufacturing factory is cut into a size of a product used in a camera. This shaving was particularly generated in a light-sensitive material having a hydrophilic colloid layer such as gelatin on the back surface, and improvement has been desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color light-sensitive material having a back layer composed of a hydrophilic colloid, which is free from troubles in which chips are not mixed in during cutting.

[0005]

The above object of the present invention has been achieved by the following constitution.

(1) At least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one blue-sensitive silver halide emulsion layer are provided on one side of the support,
A color light-sensitive material having a back surface layer on the other side, wherein the back surface layer is cured with an epoxy hardener.

(2) The color light-sensitive material as described in (1) above, wherein the back layer contains gelatin as a main binder.

(3) At least one silver halide emulsion layer
The color light-sensitive material as described in (1) or (2) above, which contains one kind of lipophilic photographic additive.

(4) The color photographic material as described in (3) above, wherein the lipophilic photographic additive is a coupler and a high-boiling organic solvent.

(5) The coating amount of gelatin in the back layer is 5 to 1
The color light-sensitive material as described in (2) above, wherein the color light-sensitive material is 5 g / m ² .

(6) At least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one blue-sensitive silver halide emulsion layer are provided on one side of the support.
A color photosensitive material having a backside layer on the other side, wherein a conductive layer is provided on the support side of the backside layer, and the backside layer is cured by an epoxy hardener. .

(7) The surface resistivity of the conductive layer is 23 ° C. 2
The silver halide color photographic light-sensitive material as described in (6) above, which has a resistance of 10 ¹² Ωcm or less under the condition of 0% RH.

(8) The above-mentioned (6) or (7), wherein the conductive layer contains at least one metal oxide.
The color light-sensitive material described in 1.

(9) The color light-sensitive material as described in (6) or (7) above, wherein the conductive layer contains a reaction product of at least one water-soluble conductive polymer and a crosslinking agent.

(10) The color light-sensitive material as described in (6) or (7) above, wherein the conductive layer contains at least one π-electron conductive polymer.

(11) The color light-sensitive material as described in (6) or (7) above, wherein the conductive layer contains at least one kind of polymer ionic solid electrolyte.

(12) The color light-sensitive material as described in (1) above, wherein the support is polyester.

(13) The color light-sensitive material as described in (12) above, wherein the polyester is polyethylene terephthalate or polyethylene naphthalate.

The inventor of the present invention can suppress the generation of chips by using an epoxy type hardener as the hardener for the back layer, and further impart the conductivity by imparting conductivity to the back layer. I found that.

The present invention will be described in detail below.

In the present invention, the epoxy hardener used for curing the back layer has a molecular weight of 100 to 1500.
And 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 used in an amount of 0.001 to 0.
It is preferably used in the range of 5 g, and more preferably 0.005 to 0.3 g.

As a method of curing the back layer with an epoxy hardener, a method of adding an epoxy hardener to the coating liquid for the back layer in advance, or an epoxy hardener at the same time during the coating of the coating liquid And a method of applying an epoxy-based hardener after the application of the coating solution and before the completion of drying, any of which can be preferably used in the present invention.

A hydrophilic colloid is preferred as the binder forming the back layer which is cured with the epoxy hardener of the present invention. Gelatin is particularly preferable as the hydrophilic colloid forming the back layer of the present invention. As the gelatin, both alkali-processed gelatin and acid-processed 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 polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone and dextran sulfate.

The amount of gelatin used in the back layer of the present invention is preferably 5 to 15 g / m ² in terms of planarity and drying properties, particularly preferred 7~13g / m ^2.

Also, the swelling ratio of the back layer is preferably 200 to 300% from the viewpoints of flatness and drying property, and 210
~ 290% is particularly preferred. The swelling ratio is a value calculated by obtaining the amount of water absorption per 1 g of the back surface layer at 38 ° C. for 3 minutes by the following formula.

Swelling rate (%) = 100+ (water absorption / backside layer weight) × 100 The silver halide emulsion layer of 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 1
Examples thereof include couplers described in 001 to 1002 and RD17643.

The relevant description locations of the RD are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C to G item 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 organic solvent, a boiling point of 130 ° C. or higher, 400 ℃
The following are preferred, and more than 150 ° C., 35
It is preferably 0 ° C. or less.

Concretely, phthalic acid esters such as dioctyl phthalate, phosphoric acid esters such as tricresyl phosphate, epoxy compounds described in JP-A-5-197099 and 5-119448, and JP-A-4-265975. Examples thereof include alcohols and amides described in JP-A-5-188547.

The 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
If it is less than Ωcm, the effect is great. As the surface resistivity becomes smaller, the inclusion of chips is suppressed, but it is 10 ⁵ Ωcm or more due to the property of the compound.

Hereinafter, a conductive layer containing metal oxide particles, a conductive layer containing a reaction product of a water-soluble conductive polymer and a crosslinking agent, a conductive layer containing a π-electron conductive polymer, and The conductive layer containing the molecular ion solid electrolyte will be described in detail in order.

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 mainly produced 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 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 .

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

As an example of the third method, in a vacuum evaporation method for obtaining metal oxide fine particles by evaporating a metal in an oxygen atmosphere, a method of keeping the amount of oxygen insufficient, or not supplying oxygen sufficiently There is a method of heating metals and metal salts.

The conductive metal oxide particles of the present invention may be crystalline or amorphous.

In the conductive layer of the present invention, conventionally known polymers can be used as a part or all of the binder. Examples of these compounds include gelatin, polyvinyl alcohol, polyvinylbenzene sulfonates, polyvinylbenzyltrimethylammonium chloride, U.S. Pat. Nos. 4,108,802 and 4,118,231.
Quaternary salt polymers described in U.S. Pat. Nos. 4,126,467 and 4,137,217, and US Pat. No. 4,070,189.
No., OLS 2,830,767 (US Ser. 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 as a layer is improved. 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 of the present invention will be described.

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

[0056]

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[0057]

[Chemical 4]

In the above P-1 to P10, Mn represents a number average molecular weight and is a value measured by GPC in terms of polyethylene glycol.

In the water-soluble conductive polymer layer of the present invention,
Hydrophobic polymer particles may be included. 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. Particularly, it is preferable that at least 30 mol% of styrene derivative, alkyl acrylate and alkyl methacrylate be contained. Particularly, 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 molecular weight of the hydrophobic polymer may be 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.

[0063]

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[0064]

[Chemical 6]

As the crosslinking agent used with the water-soluble conductive polymer of the present invention, a polyfunctional aziridine or epoxy compound is preferable. The aziridine compound is preferably a bifunctional or trifunctional compound having a molecular weight of 700 or less.

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

[0067]

[Chemical 7]

As the above-mentioned epoxy compound, those containing a hydroxyl group or an ether bond are preferable. 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 preferred specific examples of the epoxy hardener used for curing the back surface layer.

The coating amount of the water-soluble conductive polymer of the present invention is 100 to 2000 mg / m ² , preferably 200.
˜1500 mg / 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 of the present invention is a conjugation having 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. It is a 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 bonded to develop a conjugated system, 4) Heteroatom-containing conjugated systems: Polymers in which an aliphatic or aromatic conjugated system such as polyaniline is bonded to a heteroatom, 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)
Double-chain conjugated system: A conjugated system that has multiple conjugated chains in the molecule,
Polymers having a structure close to that of an aromatic conjugated system, 7) Metal phthalocyanine system: Metal phthalocyanines or polymers in which these molecules are bound by a hetero atom or a conjugated system,
8) Conductive composite: Examples include a polymer obtained by graft-copolymerizing the conjugated polymer chain with a saturated polymer, and a composite obtained by polymerizing the conjugated polymer in a saturated polymer. It can be applied to the present invention as a π-electron conductive polymer.

When the above-mentioned π-electron type conductive polymers are shown below as a polymer group, 1) means polyacetylene, poly (1,6-heptadiene) etc., and 2) means:
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 polymer having a side chain through a connecting group
Examples thereof include electronically conductive polymer composites.

Among the above, the heterocyclic conjugated system of 3), 4)
The heteroatom-containing conjugated system of 5), the mixed conjugated system of 5), 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)
Alternatively, a polymer having a repeating unit represented by ASP (V) is particularly preferable in the present invention.

[0076]

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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.

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

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 3,0.
00.

The method for 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.Chem.Commun.,
Volume 1983, p. 854, J. Polym. Sci. Polym. Lett. Ed., Volume 18, 9
Page (1980), J. Chem. Soc. Chem. Commun. 1986, 1348, Po.
lymer 27, 455 (1986), Synthetic Metals, 26, 38
3 (1988), Polymer Commun., 28, 229 (1987) and the like, and can be synthesized by these.

As a dopant for a π-electron conductive polymer
For halogen molecules (Cl₂, Br₂, I₂, ICl, I
Cl₃, IBr, IF, etc.), Lewis acid (PF_Five, AsF_Five,
SbF_Five, BF₃, BCl₃, BBr₃, SO₃Etc.), professional
Tonic acid (HF, HCl, HNO₃, H₂SO_Four, HCl
O_Four, FSO₃H, ClSO₃H, CF₃SO₃H, various
Organic acids, amino acids, etc., transition metal compounds (FeCl₃, F
eOCl, TiCl_Four, ZrCl_Four, HfCl_Four, Nb
F_Five, NbCl_Five, TaCl_Five, MoF_Five, MoCl_Five, W
F₆, WCl₆, LnCl₃(Ln = La, Ce, Pr,
Lanthanoids such as Nd and Sm), electrolyte anions
(Cl^-, Br^-, I^-, ClO_Four ^-, PF₆ ^-, AsF₆ ^-,
SbF₆ ^-, BF_Four ^-, CF₃SO₃ ^-, CF₃CO₂ ^-, CH₃
SO₃ ^-, CH₃C₆H_FiveSO₃ ^-Etc.), polymer electrolyte ani
ON (polyvinyl sulfate, polystyrene sulfonic acid, poly
(P-vinylbenzyl sulfonic acid), polyacrylic acid,
Polyethylene sulfonic acid, polyvinyl sulfonic acid, poly
Phosphoric acid, polyaspartic acid, etc.), etc.₂, X
eOF_Four, (NO₂ ⁺) (SbF₆), (NO₂ ⁺) (SbC
L₆ ^-), (NO₂ ⁺) (BF_Four ^-), FSO₂OOSO₂F,
AgClO_Four, H₂IrCl₆, La (NO₃)₃・ 6H₂O
However, the present invention is not limited to these. This
Among these, I₂, Br₂, HCl, H₂SO_Four, AsF
_Five, SbF_Five, KBF_Four, LiBF_Four, (C₂H_Five)_FourNB
F_Four, FeCl₃, LiClO_Four, CF₃SO₃Li, CF₃
SO₃Na, CF₃SO₃H, LiBr, p-toluene
Rufonic acid, polystyrene sulfonic acid, etc. are preferably used.
Be done.

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 is also available. Good.

As the doping method, for example, doping can be performed by allowing a dopant to exist in the polymerization field of the π-electron 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 doping dopant is preferably present in an amount of 1 mol% or more per repeating unit of the π-electron-type 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 type conductive polymer of the present invention and the dopant are shown below.

[0086]

[Chemical 9]

[0087]

[Chemical 10]

[0088]

[Chemical 11]

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 unit, polypropylene oxide unit, polymethyl vinyl ether unit, polystyrene sulfide unit, 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.

[0092]

[Chemical 12]

[0093]

[Chemical 13]

[0094]

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[0095]

[Chemical 15]

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.

Further, among the above-mentioned polymers having polyethylene oxide units, vinyl polymers such as P-9 to P11 and P13 may be copolymerized with other copolymerizable vinyl monomer (A). Good.

The other vinyl monomer (A) is not particularly limited, and examples thereof include 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.

[0100]

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[0101]

[Chemical 17]

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

[0103]

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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.
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, tetrahalogenated boronic acid or hexahalogenated 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 it is less than 0.01 equivalent, it is difficult to obtain a high electric conductivity, complex formation with the polymer X is insufficient, and if it exceeds 1 equivalent, it is difficult to uniformly dissolve it.

In order to add the metal salt Y to the polymer X and dissolve it, the metal salt Y may be added directly to the polymer X and, if necessary, dissolved by stirring, but it may be dissolved in 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.

By coating and drying the uniform solution thus prepared, the conductive layer of the present invention is formed.

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

Red sensitivity of the color light-sensitive material of the present invention,
As the silver halide emulsion of each of the green-sensitive and blue-sensitive silver halide emulsion layers, those described in RD308119 can be used. The description is shown below.

[Item] [Page of RD308119] Iodine composition 993 IA Item Manufacturing method 〃 〃 and 994 E Item Crystal habit (normal crystal) 〃 〃 Crystal habit (twin crystal) 〃 Epitaxial 〃 〃 Halogen composition (uniform) 993 IB term Halogen composition (not uniform) 〃 〃 Halogen conversion 994 IC term Halogen substitution 〃 〃 Metal-containing 994 ID term Monodisperse 995 IF term Solvent addition 〃 〃 Latent image formation position (surface) 995 IG term Latent image formation position (internal) ) 〃 〃 Applicable sensitizer (negative) Item 995 IH Applicable sensitizer (positive) 〃 〃 Using emulsion mixture 〃 IJ item Desalination 〃 -A Item Red-sensitive, green-sensitive and blue possessed by the color light-sensitive material of the present invention The silver halide emulsion of each sensitive 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 means 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, may be an emulsion dispersion,
It may be a solid fine particle dispersion. Among these, solid fine particle dispersion liquid in water or an organic solvent is preferable, and particularly,
A solid sensitizing dye dispersion in water is preferred.

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 onto the surface of the silver halide grain, and it is merely added for dispersion. 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 is substantially free of 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 dispersions do not substantially contain 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 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
Since it becomes non-uniform, it was found that the dispersion sedimented after the dispersion was completed, or when the dispersion was added to the silver halide emulsion, the adsorption process of the dye to the silver halide was hindered.
Further, if the solubility is higher than this range, the viscosity of the dispersion increases more than necessary, air bubbles are entrapped, which hinders the dispersion, and even higher solubility makes dispersion impossible. It has become clear from the research conducted by the present inventors.

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

Add 30 mL of ion-exchanged water to a 50 ml Erlenmeyer flask.
Add 1 ml of the dye, add an amount of the dye that does not completely dissolve it visually, and keep it at 27 ° C in a thermostatic bath and use a magnetic stirrer to
Stir for 0 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.].

By this, Lambert-Beer's law D
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 refers to a substance that 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.

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 speed during dispersion requires a long time to obtain a desired particle diameter at a low rotation speed, and entrains bubbles at a high rotation speed to lower the dispersion efficiency, so that it is 1000 to
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" refers to a suspension of a sensitizing dye, preferably having a spectral sensitizing dye weight ratio of 0.2 to 5.0% in the suspension. Is used.

The dispersion of the above-mentioned 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 listed 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 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C, XIII-C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter Dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 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. 4,4,411 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 immobilized by reacting with the formaldehyde described in No. 11,987 and No. 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. Examples of the support for the color light-sensitive material of the present invention include RD17643, page 28, R
D18716 pp. 647-8 and RD308119 XI
The supports described under X can be used.

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

The color light-sensitive material of the present invention has the above-mentioned RD3.
An auxiliary layer such as a filter layer or an intermediate layer described in the item 08119VII-K can be provided.

The color light-sensitive material of the present invention is RD30 described above.
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in Item 8119VII-K can be adopted.

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 color light-sensitive material of the present invention has the above-mentioned RD176.
43 pages 28-29, RD18716 pages 615 and R
It can be developed by the usual method described in XIX of D308119.

[0142]

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 Silver iodide fine grain emulsion SMC-1 Preparation of 5% of a 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide was vigorously stirred while 7.06 mol of silver nitrate aqueous solution and 7.06 mol of potassium iodide aqueous solution, each of which was 2 l for 10 minutes. Was added. During this period, the pH was controlled to 2.0 using nitric acid and the temperature was controlled to 40 ° C. After the particles were prepared, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution. The average grain size of the obtained silver iodide fine grains is 0.05 μm.
Met. This emulsion is called SMC-1.

Preparation of Emulsion Em-1 4.5 wt% containing 0.178 mol of seed crystal Emulsion-1 and 0.5 ml of 10% ethanol solution of polyisopropylene-polyethyleneoxy-disuccinate sodium salt. After keeping 700 ml of the aqueous solution of inert gelatin in 75 ° C. at 75 ° C. and adjusting pAg to 8.3 and pH to 5.0, grain formation was performed 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 product was washed with water at 40 ° C. using a normal flocculation method, and then gelatin was added to redisperse 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 following sensitizing dyes SD-9, SD-10 and SD-11 was weighed and 50 ml of water preliminarily adjusted to 27 ° C.
Add 3500 with a high-speed stirrer (dissolver).
By stirring at rpm for 30 to 120 minutes, a sensitizing dye solid dispersion liquid (S) having an average particle diameter of 0.38 μm (S
DA) was obtained.

Preparation of Sensitizing Dye Methanol Solution SD-B 200 mg each of the sensitizing dyes SD-9, SD-10 and SD-11 described below were weighed, and 100 ml of methanol preliminarily adjusted to 27 ° C. was added and dissolved at 27 ° C. A methanol solution of the sensitizing dye (SD-B) was obtained.

Sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to the above emulsion Em-1 using the above-mentioned solid dispersion of sensitizing dye SD-A and solution SD-B of sensitizing dye, and the fog was formed according to a conventional method. Chemical sensitization was performed to optimize the sensitivity relationship. Preparation of Support Having Conductive Layer After a polyethylene terephthalate support having a thickness of 180 μm was subjected to corona discharge treatment, a subbing first layer having the following composition was 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 Back layer side subbing 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 Cross-linking agent HA-2 10 mg / m ² Further, a corona discharge treatment was applied on the undercoating first layer, and then an undercoating second layer having the following composition was applied and dried at 100 ° C.

Emulsion layer side subbing second layer Polyco (styrene-maleic acid half ester of fluorinated alcohol) 10 mg / m ² anionic surfactant 2 mg / m ² crosslinker 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 subbing second layer (conductive layer) Polyco (sodium styrenesulfonate-maleic acid) Water-soluble conductive polymer P-3 600 mg / M ² Latex of hydrophobic polymer L-5 Average particle size 0.08 μm 300 mg / m ² Epoxy hardener (crosslinking agent) HE-5 100 mg / m ^{2 At} 140 ° C. after coating and drying the second subbing layer. Heat treatment was performed for 2 minutes.

For comparison, an undercoated support was prepared in which the backside second undercoating second layer was replaced with the emulsion layer side undercoating second layer instead of the backside layer side undercoating second layer.

Further, a subbing-completed support provided with the following backing layer-side subbing second layer (type and amount of metal oxide fine particles are shown in Table 1) instead of the backing layer-side subbing second layer, And a subbing support having the following backing layer side subbing second layer (type and amount of π-electron conductive polymer are shown in Table 1) instead of the backing layer side subbing second layer was prepared. .

Subbing second layer on back layer side (containing metal oxide fine particles) SnO ₂ particles (SnO ₂ / Sb = 85/15; volume resistance 10 ⁷ Ωcm, average particle diameter 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 Back layer second layer (π electron system) Conductive polymer content) 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) -6, those that have been ground to an average particle size of 0.15μm) 0.3g / m ² dura Agent (H-1) aqueous solution (solid content 0.5 ) 0.001 g / m ² or more layers of the following composition on a subbed support and Coating from sequential support side slide hopper to produce a color light-sensitive material samples 1 to 14.

The coating amount is the amount of silver halide and colloidal silver expressed as g / m ² in terms of metallic silver.
The amounts of couplers, additives and gelatin added in g / m ² units are shown, and the amounts of sensitizing dyes are shown in 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) 1.5 × 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 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 × 10 ^-4 Cyan coupler (C-1) 0.27 Colored cyan coupler (CC-1) 0.04 DIR compound (D-2) 0.0 1 High boiling point 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) 0.25 Colored magenta coupler (CM-1) 0.11 DIR compound (D-1) 0.004 DIR compound (D-3) 0.013 High boiling solvent (Oil-2) 0.49 Gelatin 1.10 8 layer: medium-speed green-sensitive layer silver iodobromide emulsion B 0.55 sensitizing dye (SD-1) 5.2 × 10 -4 sensitized color (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 Sensitizing dye (S-11) 1.4 × 10 ⁻⁴ Sensitizing dye (S-5) 1.5 × 10 ^-4 Sensitizing dye (S-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 1.0 0 12th layer: Intermediate layer Gelatin 0.50 13th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.16 Silver iodobromide 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 solvent (Oil-2) 0.18 Gelatin 1.19 14th layer: Medium 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) 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 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 Back layer composition Back layer 1st layer Gelatin 7 Back layer 2nd layer Gelatin 1 Anionic surfactant (Su-1) ) 0.006 Polymethylmethacrylate having an average particle size of 3 μm 0.04 Epoxy hardener of the present invention Table 1 Table 1 In addition, the above-mentioned light-sensitive materials further include compounds SU-1 and SU-
2, SU-3, SU-4, viscosity modifier, hardener H-1,
H-2, stabilizer ST-1, antifoggant AF-1, AF
-2 (weight average molecular weight 10,000 and 1,100,0
00), dyes AI-1, AI-2, AI-3, F
S-1, FS-2 and compound DI-1 were appropriately added to each layer.

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

Emulsion name Average AgI Average grain size Crystal habit Diameter / content (mol%) (μm) Thickness ratio Emulsion A 8.0 0.42 Normal crystal 1 Emulsion B 8.0 0.55 Normal crystal 1 Emulsion C 8.0 0.75 Twin crystal tabular 2 Emulsion D 2.0 0.32 Normal crystal 1 Emulsion E 8.0 0.90 Twin crystal tabular 2 Emulsions A and D contain 1 × 10 ⁻⁷ mol / l mol Ag of iridium.

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

[0163]

[Chemical 19]

[0164]

Embedded image

[0165]

[Chemical 21]

[0166]

[Chemical formula 22]

[0167]

[Chemical formula 23]

[0168]

[Chemical formula 24]

[0169]

[Chemical 25]

[0170]

[Chemical formula 26]

[0171]

[Chemical 27]

[0172]

[Chemical 28]

With respect to the above color light-sensitive material samples 1 to 14, the inclusion of chips was evaluated by the following method, and the surface resistivity was measured.

Evaluation of mixed chips The above sample was processed into a product form at a product processing factory, and mixed chips were evaluated.

The product processing was performed in the process of manufacturing a product (Konica Color Professional Film 160 Type S) containing 20 sheets of 4 × 5 inch sheet film.

The number of chips mixed in was shown by the number of deposits of 50 μm or more attached to the emulsion layer side surface of 100 sheet-like films. The number was visually counted using a 10-fold loupe.

Surface resistivity A sample coated with a conductive layer was applied to a teraohm meter (Kawaguchi Electric Co., Ltd .: Model VE-) in an atmosphere of 23 ° C. and 25% RH.
30).

The above results are shown in Table 1.

[0179]

[Table 1]

From Table 1, it can be seen that the color light-sensitive material of the present invention has improved chip generation characteristics in cutting the light-sensitive material in the light-sensitive material manufacturing process.

[0181]

According to the present invention, in a color photosensitive material having a magnetic recording layer on the back surface side, scratches on the surface of the photosensitive material are generated without deteriorating photographic characteristics and magnetic information reading accuracy. And the occurrence of blocking in the rolled state of the treated film is improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/85 G03C 1/85 7/00 510 7/00 510

Claims (13)

[Claims] 1. A support having, on one side thereof, at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, and the other side thereof. A silver halide color photographic light-sensitive material having a back layer, wherein the back layer is cured with an epoxy hardener. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the back layer contains gelatin as a main binder. 3. The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the silver halide emulsion layer contains at least one lipophilic photographic additive. 4. The silver halide color photographic light-sensitive material according to claim 3, wherein the lipophilic photographic additive is a coupler and a high boiling point organic solvent. 5. The coating amount of gelatin of the back layer is 5 to 15 g.
^{3. The} silver halide color photographic light-sensitive material according to claim ^2, which is / m ² . 6. A support has at least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one blue-sensitive silver halide emulsion layer on one side, and the other side. In a silver halide color photographic light-sensitive material having a back layer, a conductive layer is provided on the support side of the back layer,
A silver halide color photographic light-sensitive material characterized in that the back layer is further hardened with an epoxy hardener. 7. The surface resistivity of the conductive layer is 23 ° C. 20%
7. The silver halide color photographic light-sensitive material according to claim 6, which has a resistance of 10 ¹² Ωcm or less under RH conditions. 8. The silver halide color photographic light-sensitive material according to claim 6 or 7, wherein the conductive layer contains at least one metal oxide. 9. The silver halide color photographic light-sensitive material according to claim 6 or 7, wherein the conductive layer contains a reaction product of at least one water-soluble conductive polymer and a crosslinking agent. 10. The silver halide color photographic light-sensitive material according to claim 6 or 7, wherein the conductive layer contains at least one π-electron conductive polymer. 11. The silver halide color photographic light-sensitive material according to claim 6 or 7, wherein the conductive layer contains at least one kind of polymer ionic solid electrolyte. 12. The silver halide color photographic light-sensitive material according to claim 1, wherein the support is polyester. 13. The silver halide color photographic light-sensitive material according to claim 12, wherein the polyester is polyethylene terephthalate or polyethylene naphthalate.