JP3448718B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material excellent in charging property, film-forming property and transparency, and a silver halide having a magnetic recording layer excellent in mechanical strength and adhesion to a magnetic head. The present invention relates to a photographic light-sensitive material.

[0002]

2. Description of the Related Art When a silver halide photographic light-sensitive material is charged, there is a problem that the commercial value of photographic prints is impaired due to the adhesion of dust due to static electricity. In order to prevent such an obstacle, a method of forming a conductive layer containing a conductive substance has been conventionally known.

As the conductive substance, it is preferable that the conductive substance has little humidity dependency and has a good charging property even after the development processing. A typical example of such a conductive material is a crystalline metal oxide as described in JP-A-56-143431.

However, in the crystalline metal oxide, fine cracks, that is, cracks are generated in the layer containing the crystalline metal oxide, and the transparency is impaired, the conductivity is deteriorated, and the layer containing the crystalline metal oxide is fragile and easily broken. Therefore, there is a drawback that the adhesiveness with the adjacent layer is poor.

On the other hand, there has been proposed a method of recording various information on a photographic light-sensitive material by providing a magnetic recording layer on the photographic light-sensitive material. For example, a stripe-shaped magnetic recording layer in which ferromagnetic fine particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and shooting conditions. -62627, 49-4503
No. 3,243,376, 3,220,843, etc., and the back surface of the photographic light-sensitive material is transparent with the required transparency by selecting the amount and size of magnetizable particles. Providing a magnetic recording layer is described in US Pat.
No. 947, No. 4,279,945, No. 4,302,523. U.S. Pat.No. 4,947,196
The specification and International Publication WO 90/04254 describe a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material that enables magnetic recording on the back surface of a photographic film. .

In a silver halide photographic light-sensitive material having such a magnetic recording layer, film peeling due to contact between the magnetic head and the magnetic recording layer at the time of inputting / reproducing a magnetic signal, or charging of the photographic light-sensitive material There was a problem that an error occurred.

For this reason, the silver halide photographic light-sensitive material having a magnetic recording layer is more required than the ordinary silver halide photographic light-sensitive material in terms of film-forming property and charging property. In particular, if the charging property after the development processing is insufficient, a larger problem may occur.

A support used for a silver halide photographic light-sensitive material having a magnetic recording layer must have sufficient mechanical strength and have good contact with a magnetic head. .

In recent years, there has been a demand for miniaturization of cameras. In order to achieve this, it is necessary to reduce the thickness of the support, but by reducing the film thickness, the mechanical strength of the support decreases, and in some cases, obstacles such as breakage from the perforation part. Occurs. Therefore, it is necessary to increase the mechanical strength of the support from the viewpoint of downsizing the camera.

As a photographic support conventionally used, a cellulose film such as triacetyl cellulose (hereinafter sometimes abbreviated as TAC) and a polyester film such as polyethylene terephthalate are typical. In particular, polyethylene terephthalate film has an advantage that it has mechanical strength superior to that of TAC film. However, when a polyethylene terephthalate film is used as a support for a silver halide photographic light-sensitive material having a magnetic recording layer, it has a drawback that the wound curl once attached can hardly be removed even after development processing. Therefore, when the winding curl is very large, the contact with the magnetic head may not be sufficiently maintained.

[0011]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in charging property, film-forming property and transparency, and particularly excellent in charging property after development processing. There is a thing.

A second object of the present invention is to have sufficient mechanical strength, to maintain sufficient adhesion between the magnetic recording layer and the magnetic head, and to prevent errors during input and reproduction of magnetic signals. Another object of the present invention is to provide a silver halide photographic light-sensitive material having a magnetic recording layer whose occurrence is reduced and reliability of magnetic recording is enhanced.

[0013]

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

(1) In a photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support,
At least one side of the support has a layer containing a latex having a sulfonic acid group, and conductive metal oxide particles in the latex-containing layer , the sulfonic acid group
5% or more and 50% or less in terms of volume fraction with respect to the latex
A silver halide photographic light-sensitive material characterized by being contained in the range of .

(2) The halogenation according to (1) above, wherein the amount of the sulfonic acid group contained in the latex having the sulfonic acid group is 0.5 to 10 wt% with respect to the binder of the latex layer. Silver photographic light-sensitive material.

[0016]

[0017] (3) above, characterized in that at least one layer having a magnetic recording layer (1) is also properly is (2) The silver halide photographic material as claimed.

( 4 ) The support comprises a polyester layer,
A photographic support comprising the polyester layer containing, as a copolymerization component, an aromatic dicarboxylic acid having a metal sulfonate group, and / or a polyalkylene glycol, and / or a saturated aliphatic dicarboxylic acid is used. above, which (1), (2) is also properly (3) the silver halide photographic material as claimed.

( 5 ) A polyester film having a multi-layer structure, wherein at least one layer of the polyester film has, as a copolymerization component, an aromatic dicarboxylic acid having a metal sulfonate group, and / or a polyalkylene glycol,
And / or a photographic support containing a saturated aliphatic dicarboxylic acid is used, (1) and (2 ) above
The silver halide photographic light-sensitive material even properly is (3), wherein.

[0020] (6) above, characterized in that a polyester film comprising a polyester mainly composed of naphthalene dicarboxylic acid and ethylene glycol as a photographic support (1), (2) is properly described (3) Silver halide photographic light-sensitive material.

The present invention will be specifically described below. First, the metal oxide particles in the present invention will be described.

The composition of the metal oxide includes oxygen-rich oxides such as Nb ₂ O _{5 + X} , oxygen-deficient oxides such as RhO _2-X and Ir ₂ O _3-X , and Ni (OH) _X. Non-stoichiometric hydroxide, or HfO
₂ , ThO ₂ , ZrO ₂ , CeO ₂ , ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In
₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Nb, Ta etc. to TiO ₂ , and addition of Sb, Nb, halogen element etc. to SnO ₂ . Addition is effective. Addition amount of these heteroatoms is 0.01 mol% to 2
The range of 5 mol% is preferable, but the range of 0.1 mol% to 15 mol% is particularly preferable.

The particle size of the metal oxide particles used in the present invention is not particularly limited, but the size of the primary particles is 10 μm.
It is preferably m or less, more preferably 5 μm, and further preferably 1 μm or less. As a method for measuring the particle size, it is preferable to adopt an average particle diameter obtained by measurement with a particle size distribution meter such as a sedimentation method or a laser diffraction method.

The volume resistivity of these metal oxide particles is preferably 10 ¹⁰ Ωcm or less, more preferably 10 ⁷ Ωcm.
Or less, more preferably 10 ⁵ Ωcm or less.

With respect to the value of volume resistivity, in the case of an oxide from which a large single crystal can be obtained, it means the value of the volume resistivity of the single crystal, and when a large single crystal cannot be obtained, powder is formed. It means the volume resistivity of the sintered body obtained by the above. When these values are unknown, a value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure in the powder state by 10 ² is adopted. The constant pressure is not particularly limited, but a pressure of 10 kg / cm ² or more is preferable, and a pressure of 100 kg / cm ² or more is more preferable. With respect to the pressure applied to the powder and the volume resistivity of the molded body, generally, the higher the pressure, the lower the volume resistivity. However, even when an isostatic pressure of 3 t / cm ² is applied by a hydrostatic pressure device, the value is about 100 times higher than the volume resistivity value obtained with a single crystal. Therefore, a value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure in the powder state by 10 ² is adopted.

Next, the layer containing the latex having a sulfonic acid group will be described. Examples of the latex having a sulfonic acid group include polyester latex and polyvinyl latex. The means for incorporating a sulfonic acid group into the latex is not particularly limited, and examples thereof include a method of incorporating at least one monomer having a sulfonic acid group and polymerizing the latex.

The latex having a sulfonic acid group used in the present invention can be easily produced by various commonly known methods. For example, in the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of a monomer, 0.05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant are used. About 30-100 ℃, preferably 60-90 ℃
It is obtained by polymerizing under stirring for 3 to 8 hours.
The concentration of the monomer, the amount of the initiator, the reaction temperature, the time, etc. can be changed widely and easily.

Examples of the initiator include water-soluble peroxides and water-soluble azo compounds.

Examples of the dispersant include anionic surfactants, nonionic surfactants and water-soluble polymers. However, the water-soluble polymer is preferably one in which at least one of hydrophilic groups is a sulfonic acid group.

The polyester constituting the polyester latex is one having a repeating unit of a dicarboxylic acid and a diol as a main constituent. Examples of the dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the diol include ethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol and diethylene glycol.
Examples of the monomer having a sulfonic acid group used in the polyester latex include 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, 4-sulfoisophthalic acid,
And alkali metal salts thereof (for example, sodium, potassium, etc.) and the like.

Examples of the vinyl monomer constituting the polyvinyl latex include conjugated dienes such as butadiene and isoprene, non-conjugated dienes such as 1,4-pentadiene and 1,4-hexadiene, vinyl fragrances such as styrene and methylstyrene. Group, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, and acrylamides such as acrylamide, methyl acrylamide and ethyl acrylamide. Further, if necessary, a crosslinkable vinyl monomer such as glycidyl acrylate or glycidyl methacrylate can be used. Further, as the monomer having a sulfonic acid group used in the polyvinyl latex, for example, styrene sulfonic acid,
Examples thereof include vinylbenzyl sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylethane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and alkali metal salts thereof (eg sodium, potassium, etc.). .

In the latex-containing layer of the present invention,
A binder other than latex having a sulfonic acid group,
It may be included within a range that does not impair the effects of the present invention.

As the binder which can be used in the present invention,
For example, Research Disclosure No.17643, page 26,
And water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters described in No. 18716, page 651.

The amount of sulfonic acid groups contained in the latex having sulfonic acid groups is 0.5 to 10% by weight, more preferably 1 to 10% by weight based on the total weight of the binder in the layer containing the latex having sulfonic acid groups. %, More preferably 2 to 8% by weight. When the amount of the sulfonic acid group is in this range, a coating layer having excellent conductivity, film-forming property and transparency can be obtained, and the polymerization stability of the latex is good.

Here, the weight% of the sulfonic acid group with respect to the binder means the weight of sodium sulfonate contained in 100 g of the binder (unit is g), assuming that all the sulfonic acid groups of the latex are sodium salts. Represents

The average particle size of the latex having a sulfonic acid group is not particularly limited, but is preferably 0.005 to 0.8 μm, more preferably 0.01 to 0.2 μm, and further preferably 0.02 to 0.1 μm.

When the average particle size of the latex is within this range, the dispersion stability of the metal oxide particles, the conductivity of the coating film, the film-attaching property, the transparency, etc. are good.

The molecular weight is not particularly limited, but the total molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000.

In the present invention, the amount of metal oxide particles contained in the latex-containing layer of the present invention is preferably 5% or more and 50% or less, more preferably 5%, in terms of volume fraction with respect to the latex in the layer. It is 40% or less and more preferably 10% or more and 30% or less.

By using the latex having a sulfonic acid group of the present invention, as compared with the case of using a normal latex, even if a large amount of metal oxide particles are added to the latex-containing layer of the present invention, a good film formation is obtained. It was found that a coating layer having transparency and transparency can be obtained.

Here, the volume fraction of latex is
It can be calculated by the formula shown below. However, when it is difficult to directly measure each volume, a value calculated from the weight and the specific gravity can be adopted as the volume.

Volume fraction of latex (%) = {A
/ (A + B)} × 100 where A: total volume of metal oxide particles in the latex-containing layer of the present invention B: total volume of latex containing an addition polymer having a functional group in the layer as a component The coating amount is not particularly limited, but 0.05 to 2.0
It is preferably in the range of g / m ² .

The coating position of the latex-containing layer of the present invention is not particularly limited, but it is preferably coated on the side opposite to the side where the photographic constituent layer is coated on the support.

Next, the magnetic recording layer will be described.

The magnetic fine powder used in the magnetic recording layer of the present invention includes metal magnetic powder, iron oxide magnetic powder and Co.
Doped iron oxide magnetic substance powder, chromium dioxide magnetic substance powder, barium ferrite magnetic substance powder and the like can be used.

The manufacturing method of these magnetic powders is known,
The magnetic powder used in the present invention can also be manufactured according to a known method.

The shape and size of the magnetic powder are not particularly limited and can be widely used. The shape may be any shape such as a needle shape, a rice grain shape, a spherical shape, a cubic shape, or a plate shape, but a needle shape or a plate shape is preferable in terms of electromagnetic conversion characteristics. There are no particular restrictions on the crystallite size or specific surface area. The magnetic powder may be surface-treated. For example, it may be surface-treated with a substance containing an element such as titanium, silicon or aluminum, or may be adsorbed with a nitrogen-containing heterocycle such as carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester or benzotriazole. It may be treated with an organic compound such as a polar compound. The pH of the magnetic powder is not particularly limited, but it is 5-10
It is preferably within the range.

As the metal magnetic powder, for example, the metal content is 75% by weight or more, and 80% by weight or more of the metal content is a ferromagnetic metal or alloy (Fe, Co, Ni, Fe-Co, Fe-Ni, Co-N
i, Co-Fe-Ni, etc., and other components (A
l, Si, S, Sc, Ti, V, Cr, Mn, Cu, Zn, Y, Mo, R
h, Pd, Ag, Sn, Sb, B, Ba, Ta, W, Re, Au, Hg, P
b, P, La, Ce, Pr, Nd, Te, Bi, etc.) are included. Further, the above-mentioned ferromagnetic metal component is a small amount of hydroxide,
Alternatively, it may contain an oxide.

Examples of the iron oxide magnetic powder include γ-iron oxide. The ratio of divalent iron / trivalent iron in iron oxide can be used without particular limitation.

Regarding these magnetic recording layers, Japanese Patent Laid-Open No.
-32812 and 53-109604.

Regarding the size of magnetic particles, it is "television" that there is a correlation between the size and the transparency.
Volume 20, No. 2 "Characteristics of Ultrafine Particle Semi-Transparent Magnetic Recording Medium and Its Application". For example, in the acicular powder of γ-Fe ₂ O ₃ , the light transmittance is improved by reducing the particle size.

Therefore, it is preferable to make the particle size of the magnetic powder as small as possible within the range in which the required magnetic properties can be obtained. Further, if the coating amount of the magnetic particles is reduced to a certain extent or more, the required magnetic characteristics cannot be obtained, so it is preferable to reduce the coating amount within the range where the required magnetic characteristics are obtained.

Practically, the coating amount of the magnetic powder is 0.001
˜3 g / m ² , more preferably 0.01 to 1 g / m ² .

As the binder used in the magnetic recording layer, known thermoplastic resins, radiation curable resins, thermosetting resins and other reactive resins conventionally used as binders for magnetic recording media are used. Mixtures of can be used.

The thermoplastic resin has a Tg of −40 ° C. to 150 ° C., preferably 60 ° C. to 120 ° C., a weight average molecular weight of 10,000 to 300,000, and more preferably a weight average molecular weight. Is from 50,000 to 200,000.

The binder may have a polar group in its molecule. The polar group is an epoxy group, -COOM,-
_{OH, -NR 2, -NR 3 X} , -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO
₃ M (M is hydrogen, alkali metal or ammonium, X is an acid forming an amine salt, R is hydrogen,
(Representing an alkyl group).

A hydrophilic binder may also be used as the binder for the magnetic recording layer of the present invention. Examples of the hydrophilic binder that can be used in the present invention include Research Disclosure No. 17643, page 26, and No. 18716,
The water-soluble polymer, cellulose ether, latex polymer and water-soluble polyester described on page 651 can be mentioned. Of these, gelatin is the most preferable.

The gelatin may be unmodified or modified. Further, a part thereof is colloidal albumin, casein carboxymethyl cellulose, cellulose derivative such as hydroxyethyl cellulose, agar, sodium alginate, starch derivative, sugar derivative such as dextran, synthetic hydrophilic colloid, for example,
It may be replaced with polyvinyl alcohol, poly N-vinylpyrrolidone, acrylic acid copolymer, polyacrylamide or their derivatives, partial hydrolysates, gelatin derivatives and the like.

The hydrophilic binder containing gelatin is preferably hardened. Hardeners that can be used include aldehyde compounds, ketone compounds, reactive halogen-containing compounds, reactive olefin-containing compounds, and N-
Hydroxymethylphthalimide, N-methylol compound,
Examples thereof include isocyanates, aziridine compounds, acid derivatives, epoxy compounds, halogen carboxaldehydes. Inorganic hardeners can also be used.

Hardeners are typically 0. 0 for dry gelatin.
It is used in an amount of 01 to 30% by weight, preferably 0.05 to 20% by weight.

The magnetic powder is dispersed in the binder using a solvent if necessary to form a coating liquid. A ball mill, homomixer, sand mill, or the like can be used to disperse the magnetic powder. In this case, it is preferable to disperse the magnetic particles one by one as much as possible without damaging the magnetic particles.

When forming an optically transparent magnetic recording layer, the amount of the binder is 1 to 20 parts by weight based on 1 part by weight of the magnetic powder. Further, the solvent is used in such an amount that the coating can be easily performed.

As the method for providing the magnetic recording layer on the support, air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, A spray coat can be used. In order to carry out multi-stripe coating, these coating heads may be arranged in series. Specific methods of stripe coating include, for example, JP-A-48-25503, JP-A-48-25504, JP-A-48-98803, and JP-A-50-13803.
7, gazette 52-15533 gazette, gazette 51-3208 gazette, gazette 51-6
No. 239, No. 51-65606, No. 51-140703, Japanese Patent Publication No. 29-4221, U.S. Pat.No. 3,062,181, the same.
The description in the specification of 3,227,165 can be referred to.

In order to firmly adhere these magnetic recording layers to the support, an undercoat layer may be provided on the support, and the support may be subjected to chemical treatment, mechanical treatment, corona discharge treatment,
Flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment,
Surface activation treatment such as active plasma treatment, laser treatment, concentrated acid treatment, or ozone oxidation treatment may be performed. Furthermore, an undercoat layer may be provided after the surface activation treatment.

The thickness of the magnetic recording layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, still more preferably 0.5.
~ 3 μm.

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to impart functions to the magnetic recording layer such as imparting lubricity, antistatic property, antiadhesive property, and improving friction and wear characteristics. Various additives can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and for preventing clogging of the magnetic head. It is possible to add an abrasive.

If necessary, a layer for supplementing adhesion with other layers may be provided in the layer adjacent to the magnetic recording layer, or an adjacent protective layer may be provided to improve scratch resistance.

A compound generally known as a slip agent can be used for imparting scratch resistance, but higher fatty acid esters are preferable. When the magnetic recording layer is provided in a stripe shape, a transparent polymer layer containing no magnetic material may be provided thereon to eliminate the step due to the magnetic recording layer. In this case, the transparent polymer layer may have the above-mentioned various functions.

After providing the magnetic recording layer, calendering is performed on this layer to improve smoothness, and S of magnetic output is provided.
It is also possible to improve the / N ratio. In this case, it is preferable to apply the silver halide photographic light-sensitive layer after the calendering treatment.

The polyester as a material for forming the support of the present invention is one having a repeating unit of dicarboxylic acid and diol as a main constituent, and preferably a repeating unit of aromatic dibasic acid and glycol. Polyester as a main component can be mentioned.

Examples of the dibasic acid include terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and examples of the diol or glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol and 1,4-cyclohexanediene. Examples include methanol, diethylene glycol and p-xylene glycol. Of these, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents and polyethylene-2,6-naphthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents are preferable.

Further, a copolymer of two or more kinds of dibasic acids and one or more kinds of diols can be used. For example,
Examples of the polyester include terephthalic acid, 2,6-naphthalenedicarboxylic acid, and ethylene glycol as main constituents.

A blend of two or more polyesters may be used. For example, a blend of polyethylene terephthalate and polyethylene-2,6-naphthalate can be used.

Further, a copolymer containing 85 mol% or more, preferably 90 mol% or more of these main repeating units may be used as long as the original excellent properties of polyester are not impaired, and other polymers may be blended. May be done.

The intrinsic viscosity of the polyester is preferably, but not limited to, 0.45 to 0.80, and particularly preferably 0.55 to 0.70, from the viewpoint of stretchability during the production of a laminated film.

The copolymerized polyester as a material for forming the support of the present invention is preferably an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and a repeating unit of a dicarboxylic acid and a diol as a main constituent. Can be a copolyester having aromatic dibasic acid and glycol as main constituents. Furthermore, in the present invention, as the copolyester, a blend of the copolyester and the polyester can be mentioned.

Examples of the dibasic acid include terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and examples of the glycol include ethylene glycol and
Examples include propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol and p-xylene glycol. Among the copolyesters, among others, copolyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents, and copolyethylene terephthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents.
-2,6-naphthalate is preferred.

The preferred intrinsic viscosity of the copolyester is not particularly limited, but is preferably 0.35 to 0.75 from the viewpoint of stretchability during the production of a laminated film, and particularly preferably 0.
45 to 0.60 is preferable.

Aromatic dicarboxylic acids containing a metal sulfonate group as a copolymerization component in the copolyester include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoisophthalic acid and 4-sodium sulfoisophthalic acid. Examples thereof include sodium sulfo-2,6-naphthalenedicarboxylic acid or ester-forming derivatives represented by the following chemical formula 1, and compounds obtained by substituting these sodiums with other metals such as potassium and lithium.

[0080]

[Chemical 1]

The above-mentioned copolymerized polyester preferably contains polyalkylene glycol and / or saturated aliphatic dicarboxylic acid as a copolymerization component within a range that does not impair the effects of the present invention.

As the polyalkylene glycols, polyethylene glycol, polytetramethylene glycol and derivatives thereof are used. Among them, the polyethylene glycol represented by the formula (a) is preferable, and the molecular weight is not particularly limited, but is 300 to 20000. Is more preferably used, more preferably from 600 to 10,000, and particularly preferably from 1000 to 5000.

H (O—CH ₂ CH ₂ ) _n —OH (a) In addition, as the polyalkylene glycols, the terminal —H of polyethylene glycol is replaced with —CH ₂ COOR (R: H or alkyl having 1 to 10 carbon atoms). Group, n: a positive integer) and substituted with a polyethyleneoxydicarboxylic acid represented by the formula (b) or a polyether dicarboxylic acid represented by the formula (c) (R ': alkylene having 2 to 10 carbon atoms). Group, n: positive integer) and the like, the same effect can be obtained.

ROOCCH ₂ — (O—CH ₂ CH ₂ ) _n —OCH ₂ COOR (b) ROOCCH ₂ — (O—R ′) _n —OCH ₂ COOR (c) (b), (c) The molecular weight of the compound is also not particularly limited, but it is preferably 300 to 20000, more preferably 600 to 10000, and particularly preferably 1000 to 5000.

As the saturated aliphatic dicarboxylic acid, for example, its ester-forming derivative is preferable, and adipic acid, dimethyl adipate, which is an ester of sebacic acid, dimethyl sebacate, etc. are used. Dimethyl adipate is preferred.

The copolymerized polyester used in the present invention may be further copolymerized with other components or may be blended with other polymers as long as the effects of the present invention are not impaired.

-Production of Polyester and Copolyester-The polyester and copolyester used in the present invention are both phosphoric acid, phosphorous acid and their esters and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate) at the polymerization stage. , Titanium dioxide, etc.) or inorganic particles may be blended with the polymer after polymerization. Further, a pigment, an ultraviolet absorber, an antioxidant and the like may be added appropriately at any stage of the polymerization and after the polymerization.

To obtain the copolyester, the acid component and the glycol component may be transesterified, and then the above-mentioned copolymerization component may be added to carry out melt polymerization, or the copolymerization component may be transesterified. Melt polymerization may be carried out after the ester is added before the transesterification, or a known synthesis method such as solid-phase polymerization of the polymer obtained by the melt polymerization may be employed.

Examples of the catalyst used for the transesterification include acetates, fatty acid salts and carbonates of metals such as manganese, calcium, zinc and cobalt. Among these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable. It is also effective to add a metal salt of a hydroxide or an aliphatic carboxylic acid, a quaternary ammonium salt or the like within a range that does not hinder the reaction or color the polymer during the transesterification and / or the polymerization. Sodium hydroxide,
Sodium acetate, tetraethylhydroxyammonium and the like are preferable, and sodium acetate is particularly preferable.

The polyester or copolymerized polyester for forming the photographic support of the present invention may contain various additives. For example, a dye may be added to the polyester or copolymerized polyester for the purpose of preventing a light piping phenomenon (fogging) that occurs when light is incident from the edge of a photographic support coated with a photographic emulsion layer. . The type of this dye is not particularly limited, but it is preferable that it has excellent heat resistance in the film forming process, and examples thereof include anthraquinone-based chemical dyes. As for the color tone, gray dyeing is preferable as seen in general light-sensitive materials, and one kind or two or more kinds of dyes may be mixed and used.

-Layer Structure of Polyester- The layer structure of the polyester layer and / or the copolyester layer of the photographic support of the present invention may be a single layer structure composed of any of these layers, or any one of them. May have a laminated structure in which an arbitrary number of layers such as two layers, three layers, and four layers are laminated. A preferred layer structure is a multilayer structure of two or more layers. The “polyester layer” included in the support of the present invention is limited to a layer having a thickness of 2 μm or more, and a subbing layer having a thickness of less than 2 μm is not regarded as a “polyester layer”. .

-Support in which the polyester layer has a single-layer structure-When the polyester layer contained in the support of the present invention is a single layer, it is particularly preferably a copolyester layer. Here, the copolyester layer can be formed of the above-mentioned copolyester or a blend of the copolyester and the polyester.

When a single layer film is formed from the above-mentioned copolymerized polyester, the content ratio of the aromatic dicarboxylic acid containing a metal sulfonate group as a copolymerization component is 1 to 10 mol% relative to all ester bonds, particularly Preferably 2
~ 7 mol%. By setting the content of the aromatic dicarboxylic acid having a metal sulfonate group within the above range, the curl-eliminating property after the developing treatment and the curl-before the developing treatment can be made more difficult.

The thickness of the polyester layer having a single-layer structure is usually
It is 50 to 130 μm, preferably 65 to 110 μm.

The single-layer polyester film of the present invention can be manufactured as follows. That is, a method for obtaining an unstretched sheet may be a conventionally known method,
For example, a method may be mentioned in which the obtained resin is sufficiently dried, then melt-extruded in a sheet form through a filter and a die, cast on a rotating cooling drum, and cooled and solidified.

As a method for biaxially stretching the finished sheet, for example, the following processes (A) to (C) can be adopted.

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

The above-mentioned stretching means the mechanical strength of the photographic support,
In order to satisfy the dimensional stability and the like, the area ratio is preferably 4 to 16 times. Also, heat setting is 150-240 ℃
Can be performed in the temperature range of.

-Photographic Support Having Polyester Layer of Laminate Structure-When the film of the present invention has a laminate structure of two or more layers, generally the thickness of each layer is appropriately determined depending on the polyester and copolyester used. However, the ratio of the total thickness d ₅ of the copolyester layer to the total thickness d ₄ of the polyester layer is preferably 0.5 ≦ d ₅ / d ₄ ≦
3, more preferably 0.7 ≦ d ₅ / d ₄ ≦ 2, and the total thickness d ₄ of the polyester layers is preferably 50 μm or less, more preferably 40 μm or less.

The total thickness of the laminated film is not particularly limited, but is preferably 40 to 130 μm, and particularly preferably 65 to 100 μm.
If it is thinner than this range, the required strength may not be obtained in some cases, and if it is thicker, it is not superior to the conventional photographic support. Further, when the film has a laminated structure composed of a polyester layer and a copolyester layer, if the total thickness of the polyester layers exceeds 50 μm, the curl resolving property may be poor, which is not preferable.

Further, even when the laminated structure of the polyester layer is two or three layers, even in the laminated structure of four or more layers, the polyester layer of the laminated structure is centered around the position where the thickness is divided into two. When the film is divided into two parts on the laminated surface, if the layer structure above and below the divided surface is asymmetric, handling is easy, for example, when applied to a photographic film, a photographic support with excellent insertability at the entrance of a splicer processor. Become a body.

The term "asymmetrical" as used herein means that they are physically, mechanically or chemically different, and for example, the order of forming the polyester layer, the copolyester layer or layers made of other materials, the polyester layer, the copolyester. The thickness of the layer or the layer made of other materials, the amount of main constituent components constituting the polyester or copolymerized polyester above and below the surface to be divided in half is different, or the amount of the copolymerization component or the copolymerization component is different, or Means that the intrinsic viscosities are different, and that the type of the copolymerization component or the content of the copolymerization component is different in any of the respective polyester layers on the dividing surface. Examples of the method for confirming the asymmetry of these laminated polyester layers include use of various analytical instruments, and are not particularly limited, but the layer structure can be confirmed by observing the cross section of the film with a microscope, and also with a microscope. It can also be confirmed by taking a picture. Also, while observing this with a microscope, scrape off each layer, or scrape it from the top and bottom to the surface that divides it in half to obtain the upper and lower layers or the analyte of each layer, and perform hydrolysis to perform liquid chromatography. It may be measured with various measuring devices such as NMR, or after the analyte is dissolved in a solvent, NMR analysis or GPC (gel permeation chromatography)
Analysis or measurement of intrinsic viscosity may be performed, or X-ray spectroscopic analysis of the substance to be analyzed as it is with powder, or IR (infrared spectroscopic instrument) analysis by mixing with KBr etc. The asymmetry of both outer layers can be confirmed or measured by the absolute amount, the position of the peak of the measurement result corresponding to the absolute amount, the difference in intensity, or the like.

The polyester layer of the photographic support of the present invention is not limited to two layers, three layers, and four layers or more, and is not limited to these. The width of the film of the present invention should be unrolled to form a roll when the width of the film is rolled and the curl is imparted by appropriately adjusting the aforementioned items such as the amount of the copolymerization component. It is possible to further increase the effect of the present invention in that it is difficult for the curling to occur.

Further, when it has a laminated structure of two or more layers, it can be manufactured as follows. That is,
For example, polyester and copolyester are melt extruded from separate extruders, and then extruded by joining them in a laminar flow in a conduit of the molten polymer or in an extrusion die,
After cooling and solidifying on a cooling drum to obtain an unstretched film,
Method of biaxially stretching and heat setting, or polyester or copolymerized polyester simple substance, and melt-extruding a laminated film from an extruder, unstretched film cooled and solidified on a cooling drum or uniaxially oriented film uniaxially stretched the unstretched film The surface is coated with an anchor agent, an adhesive, etc., if necessary, and then the polyester or copolymerized polyester alone and the laminated film are extrusion laminated, and then the biaxially stretching is completed, and then the heat lamination is carried out. Although there are methods, etc., the coextrusion method is preferable because of the simplicity of the process.

The stretching conditions in this case are not particularly limited, but generally, from the higher glass transition temperature (Tg) of the polyester layer or the copolyester layer to Tg + Tg + 10.
It is biaxially stretched in the temperature range of 0 ° C. At this time, in the same manner as in the stretching method for the single-layer polyester layer, the above (A), (B),
The method (C) can be adopted. Stretch ratio is 4 in area ratio
It is preferably carried out in the range of up to 16 times. Also, heat fixation
It can be performed in the temperature range of 150 to 240 ° C.

Further, in order to reduce the curling of the photographic support made of polyester, JP-A-51-16358 and JP-A-51-16358.
The method described in 6-35118 or the like can be preferably used.

That is, this is a method of heat treatment at a temperature of 50 ° C. or higher and a glass transition point or lower for 0.1 to 1500 hours.

Since this heat treatment is carried out at a high temperature of 50 ° C. or higher, if it is carried out after coating the emulsion, it tends to cause deterioration of the performance of the emulsion layer. Therefore, it is desirable to do it before coating the emulsion layer.

Typical examples of the photographic light-sensitive material of the present invention include a black-and-white light-sensitive material, a color negative light-sensitive material, and a color reversal light-sensitive material.

The silver halide emulsion used in the present invention is, for example, Research Disclosure (RD) No. 17643, 22.
Pp. 23 (December 1978) "I. Emulsion preparat
ionand types) ”and the same (RD) No.18716, 648
Page, "Graphics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafkides, Chemic et Phisique Photographi
Quque, Paul Motel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra
Phic Emulsion Chemistry Focal Press 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., V.L. Zelikman et al., Making and Coating Phot
It can be prepared using the method described in ographic Emulsion, Focal Press, 1964) and the like.

Emulsions are disclosed in US Pat. Nos. 3,574,628 and 3,665,394.
Monodisperse emulsions described in U.S. Pat.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are RD No.17643, No.18716 and N.
o.308119 (hereinafter RD17643, RD18716 and RD3081 respectively
(Abbreviated as 19)). The description is shown below.

[Item] [RD308119] [RD17643] [RD18716] Chemical sensitizer, page 996, section III-A, page 23, page 648, spectral sensitizer, page 996, IV-A, B, C, D, I, J, section 23 Page 24 648-9 page Supersensitizer page 996 IV-AE, J section 23-24 page 648-9 page Antifoggant page 998 VI page 24-25 page 649 Stabilizer page 998 VI page 24-25 page 649 When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, the photographic additives that can be used are described in the above RD. The following shows the relevant locations.

[Item] [RD308119] [RD17643] [RD18716] Color turbidity inhibitor page 1002 page VII-I section 25 page 650 dye image stabilizer page 1001 VII-J section 25 whitening agent page 998 V page 24 UV light Absorber page 1003 VIII-C, XIII-C page 25-26 page Light absorber page 1003 VIII page 25-26 light scatterer page 1003 VIII filter dye page 1003 VIII page 25-26 binder 1003 page IX page 26 651 page static Inhibitor 1006 page XIII 27 page 650 Hardener 1004 page X 26 page 651 Plasticizer page 1006 XII 27 page 650 page Lubricant 1006 XII page 27 650 Activator / Coating aid page 1005 XI page 26-27 Page 650 matting agent page 1007 XVI developer (containing in photosensitive material) page 1011 XX-B When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used. Examples are given below in RD17643 and RD308119. The relevant description is shown below.

[Item] [RD308119] [RD17643] Yellow coupler page 1001 VII-D item page 25 VII-C to G item magenta coupler page 1001 VII-D item page 25 VII-C to G cyan coupler page 1001 VII- Item D Page 25 VII-C to G Item Colored Coupler Page 1002 Item VII-G Item 25 Page VII-G Item DIR Coupler 1001 Page VII-F Item 25 Page VII-F BAR Coupler Page 1002 VII-F Other useful residue Group-releasing coupler page 1001 VII-F Alkali-soluble coupler page 1001 VII-E Further, these additives can be added to the photographic light-sensitive layer by the dispersion method described in RD308119 page 1007 XIV.

For the color photographic light-sensitive material, the above-mentioned RD308119 V
An auxiliary layer such as a filter layer or an intermediate layer described in the section II-K can be provided.

In the case of forming a color photographic light-sensitive material, the above
RD308119 Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in Section VII-K can be adopted.

In order to firmly adhere these photographic constituent layers (eg, photosensitive silver halide emulsion layer, intermediate layer, filter layer, magnetic recording layer, conductive layer) to the support, an undercoat layer is provided on the support. It is not necessary to provide the support, and the support is subjected to chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatment such as laser treatment, concentrated acid treatment, or ozone oxidation treatment may be performed. Further, an undercoat layer may be provided after the surface activation treatment, and a photographic emulsion layer may be coated thereon.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James, Theory of the Photografic Process Forth Editi
on) pages 291 to 334 and the Journal of the American Chemical Society (Journal of the Ameri
can Chemical Society) Vol. 73, page 3,100 (1951), known per se can be used. Also. The color photographic light-sensitive material is the above-mentioned RD17643.
Development can be carried out by a usual method described on pages 28 to 29, RD18716 page 615 and RD308119 XIX.

[0120]

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

Example 1 <Preparation of Support> As a polyester resin for the support, support S-1 commercially available polyethylene terephthalate (intrinsic viscosity 0.65, film thickness 90 μm) support S-2 dimethyl terephthalate 100 weight Part, ethylene glycol 6
0.1 part by weight of calcium acetate hydrate was added to 4 parts by weight as a transesterification catalyst, and transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β
-Hydroxyethyl) isophthalic acid (abbreviation: SIP) ethylene glycol solution (concentration 35% by weight) 28 parts by weight (5 mol% / total ester bond), polyethylene glycol (abbreviation: PEG) (number average molecular weight), antimony trioxide 0.05
0.13 parts by weight of phosphoric acid trimethyl ester, and Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant were added so as to be 1% by weight based on the product polymer. Then gradually raise the temperature and reduce the pressure to 280 ° C and 0.5 mmHg.
Polymerization was carried out to obtain a copolyester (intrinsic viscosity of 0.
55, film thickness 90 μm).

<Tin oxide dispersion> 400 g of powder of antimony-doped tin oxide SN-100P manufactured by Ishihara Sangyo Co., Ltd. and 60 parts of water
After adjusting 0 g of the mixed solution to pH 7.0, the mixture was dispersed with a stirrer and a sand mill to prepare a dispersion A.

<Preparation of Light-Sensitive Material> The support thus prepared was subjected to an undercoating process as described below to form a back layer and an emulsion layer.

Both sides of the support were subjected to a corona discharge treatment of 8 W / (m ² · min), and one side of the support was coated with the undercoat coating solution A.
-1 is applied to a dry film thickness of 0.8 μm to form an undercoat layer A-
1 is formed on the undercoat layer A-1 and 8 W / (m ² · mi
n) is subjected to corona discharge, and the following subbing coating solution A-2 is applied onto the subbing layer A-1 to give a dry film thickness of 0.1 μm.
Formed 2.

On the other surface of the support, the following coating solution B-1 was applied.
To B-6 were coated so that the dry film thickness was 0.6 μm, to form conductive layers B-1 to B-6.

<Undercoating Coating Liquid A-1> Copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content 30 %) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating liquid A-2> Gelatin 10g Compound (UL-1) 0.2g Compound ( UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size 3 μm) 0.1 g Finish with water 1000 ml In the formulation below, LX-1 to LX-3 are latex, P
OL-1 represents a water-soluble polymer.

[0127] <Coating liquid B-1>   LX-1 aqueous dispersion (solid content 30% by weight) 270 g   Compound (UL-1) 0.6 g   Dispersion A 560g   Finish with water 1000ml <Coating liquid B-2>   LX-2 aqueous dispersion (solid content 30% by weight) 270 g   Compound (UL-1) 0.6 g   Dispersion A 560g   Finish with water 1000ml <Coating liquid B-3>   Gelatin 110g   Compound (UL-1) 0.6 g   Compound (H-1) 0.8 g   Dispersion A 560g   Finish with water 1000ml <Coating liquid B-4>   LX-3 aqueous dispersion (solid content 30% by weight) 270 g   Compound (UL-1) 0.6 g   Dispersion A 560g   Finish with water 1000ml <Coating liquid B-5>   55 g of gelatin   POL-1 55g   Compound (UL-1) 0.6 g   Compound (H-1) 0.8 g   Dispersion A 560g   Finish with water 1000ml <Coating liquid B-6>   LX-3 aqueous dispersion (solid content 30% by weight) 135 g   POL-1 41g   Compound (UL-1) 0.6 g   Dispersion A 560g   Finish with water 1000ml <LX-1>   5-sulfoisophthalic acid 5 mol%   Isophthalic acid 15 mol%   Terephthalic acid 30 mol%   Ethylene glycol 25 mol%   Diethylene glycol 25 mol%   (Average particle size 60nm) <LX-2>   2-acrylamido-2-methylpropanesulfonic acid 8 mol%   Styrene 30 mol%   Butyl acrylate 62 mol%   (Average particle size 60nm) <LX-3>   Isophthalic acid 20 mol%   Terephthalic acid 30 mol%   Ethylene glycol 25 mol%   Diethylene glycol 25 mol%   (Average particle size 60nm) <POL-1>   Acrylamide 94 mol%   Styrene sulfonic acid 6 mol%   (Average molecular weight 64,000)

[0128]

[Chemical 2]

Further, a corona discharge of 8 W / (m ² · min) was applied on the conductive layers B-1 to B-6, and the following coating layer OC-1 was applied to a dry film thickness of 1 μm. .

<OC-1> 35 parts by weight of nitrocellulose 35 parts by weight of polyurethane resin 1 part by weight of lauric acid 1 part by weight of oleic acid 1 part by weight of butyl stearate 1 part by weight of cyclohexanone 75 parts by weight of methyl ethyl ketone 150 parts by weight of toluene 150 parts by weight of the undercoating A corona discharge of 25 W / (m ² · min) was applied on Layer A-2, and the following photographic constituent layers were sequentially formed to prepare a multilayer color photographic light-sensitive material. The constitution of each support provided with the above conductive layer is shown in Table 2.

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

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

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.

[0134]

[Table 1]

The samples were simultaneously coated with a multi-slide hopper type coater at the first time from the first layer to the eighth layer, and at the second time onto the ninth layer to the fifteenth layer.
Sample 101 had a silver coating amount of 6.25 g / m ² , a dry film thickness of 18 μm, and a specific photographic speed of ISO 420.

[0136]

[Chemical 3]

[0137]

[Chemical 4]

[0138]

[Chemical 5]

[0139]

[Chemical 6]

[0140]

[Chemical 7]

[0141]

[Chemical 8]

[0142]

[Chemical 9]

[0143]

[Chemical 10]

[0144]

[Chemical 11]

[0145]

[Chemical 12]

A film was prepared by cutting each of the prepared samples to a width of 35 mm.

This film was subjected to the development processing shown below.

[0148] <Development processing>     1. Color development ・ ・ ・ 3 minutes 15 seconds 38.0 ± 0.1 ℃     2. Bleaching ・ ・ ・ ・ 6 minutes 30 seconds 38.0 ± 3.0 ℃     3. Washing with water ・ ・ ・ ・ 3 minutes 15 seconds 24-41 ℃     4. Settling ··· 6 minutes 30 seconds 38.0 ± 3.0 ℃     5. Washing with water ・ ・ ・ ・ 3 minutes 15 seconds 24-41 ℃     6. Stability ・ ・ ・ ・ 3 minutes 15 seconds 38.0 ± 3.0 ℃     7. Dryness ... 50 ° C or less The composition of the treatment liquid used in each step is shown below.

[0149] <Color developer>   4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl)     Aniline / sulfate 4.75g   Anhydrous sodium sulfite 4.25g   Hydroxylamine 1/2 sulfate 2.0g   Anhydrous potassium carbonate 37.5g   Sodium bromide 1.3g   Nitrilotriacetic acid sodium salt (monohydrate) 2.5 g   1.0 g of potassium hydroxide   Add water to make 1 liter (pH = 10.1) <Bleach>   Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g   Ethylenediaminetetraacetic acid diammonium salt 10.0 g   Ammonium bromide 150.0 g   Glacial acetic acid 10.0g   Add water to make 1 liter, and adjust to pH 6.0 with aqueous ammonia.

[0150] <Fixer>   Ammonium thiosulfate 175.0 g   Anhydrous sodium sulfite 8.5g   Sodium metasulfite 2.3g   Add water to 1 liter and adjust to pH 6.0 with acetic acid.

[0151] <Stabilizer>   Formalin (37% aqueous solution) 1.5 ml   Conidax (manufactured by Konica Corporation) 7.5 ml   Add water to make 1 liter.

Also, one randomly selected film from the developed film was prepared for each sample at 23 ° C. and 20% RH.
All 24 frames were printed and the number of dust visually observed on the print was measured. Also, the haze on the emulsion side of the support before the back layer is coated and before the photographic constituent layers are coated is JI.
Measurement was performed according to SK-6714, and the results are shown in Table 2.

Further, the obtained color negative film was provided with a film in a dry state before development (hereinafter referred to as a raw film), with a wet film under development, and with a film in a dry state after development (hereinafter referred to as dry). The results shown in Table 2 were obtained when the film-attached) was evaluated by the following method.

Evaluation method with film (with live film and dry film) A scratch reaching the support at an angle of 45 ° with a razor blade on the surface of the back layer of the sample which has been dried before or after the development process. Attached in a grid,
An adhesive tape (cellophane adhesive tape) is pressure-bonded thereon, and then the tape is rapidly peeled off at an angle of about 45 °. At this time, the area of the back layer that is peeled off together with the tape is compared with the area where the tape is stuck, and the following 5 grades are evaluated.

[0155]    Rating 5 4 3 2 1   Peeling condition None 0-20% 21-50% 51-100% 101% or more If the evaluation is 4 or more, it can be considered that the film is sufficiently strong in practical use.

(With wet film) During various development processes, scratches reaching the support were formed in a lattice pattern on the surface of the back layer of the sample with a sharp needle, and then the surface of the layer was strongly strengthened in a wet state. Rub for 10 seconds. The surface of the back layer, which is peeled off at this time, is compared with the lattice area and evaluated in five levels. The evaluation criteria are the same as with raw and dry film. The above results are shown in Table 2.

[0157]

[Table 2]

From the results shown in Table 2, according to the present invention, a film support having excellent conductivity, film-attaching property and transparency was obtained. In particular, the support S-2 and the conductive layer were B-1. Further, it can be seen that Sample 107 is a silver halide photographic light-sensitive material excellent in film forming property.

Example 2 <Preparation of support> In the same manner as in Example 1, the support S-1 was prepared.
It was created.

<Preparation of Photosensitive Material> As in Example 1, the prepared support was provided with a photographic constituent layer on one side of the support,
Apply the following coating liquid B-7 on the other side of the support,
A conductive layer B-7 was provided, and further a coating layer OC-1 was provided.

<Coating Liquid B-7> Aqueous dispersion of LX-1 ′ (solid content 30% by weight) 270 g Compound (UL-1) 0.6 g Dispersion A 560 g Finished with water 1000 ml However, what is LX-1 ′ , LX-1 modified by changing the ratio of 5-sulfoisophthalic acid and isophthalic acid to change the amount of sulfonic acid groups contained in the latex and changing the polymerization conditions. The average particle size is changed. Table 3 shows specific numerical values.

In the same manner as in Example 1, dust adhesion, film formation, and haze were measured. The results are shown in Table 3.

[0163]

[Table 3]

From the results shown in Table 3, it can be seen that the silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material excellent in conductivity, film-forming property and transparency.

Example 3 <Preparation of support> In the same manner as in Example 1, the support S-1 was prepared.
It was created.

<Preparation of Photosensitive Material> As in Example 1, the prepared support was provided with a photographic constituent layer on one side of the support,
The following coating liquids B-8 and B-9 were coated on the other side of the support to provide conductive layers B-8 and B-9, and further a coating layer OC-1 on each of them. .

<Coating Liquid B-8> Aqueous dispersion of LX-1 (solid content 30% by weight) 270 g Compound (UL-1) 0.6 g Dispersion A Appropriate amount Finish with water 1000 ml <Coating Liquid B-9> LX- Aqueous dispersion 3 (solid content 30% by weight) 270 g Compound (UL-1) 0.6 g Dispersion A Appropriate amount Finish with water 1000 ml However, in order to change the volume fraction of the metal oxide particles with respect to the latex, Adjust the amount added. Table 4 shows specific numerical values.

In the same manner as in Example 1, dust adhesion, film formation, and haze were measured. The results are shown in Table 4.

[0169]

[Table 4]

From the results shown in Table 4, it can be seen that, according to the present invention, good film-forming property and transparency are maintained even when the amount of metal oxide particles added is increased.

Example 4 <Preparation of support> In the same manner as in Example 1, the support S-1,
S-2 was created. Further, the supports TAC and S shown below
-3, S-4, and S-5 were created.

Support TAC Commercially available triacetyl cellulose (film thickness 100 μm) Supports S-3 S-1 and S-2 were vacuum dried at 150 ° C., respectively, and then two of the three extruders were used. It is used for S-2, melt-extruded at 285 ° C., and the film thickness ratio of three layers is S-2: S-1: S-2 = 1:
The layers were joined in a T-die so as to have a ratio of 1: 1 and rapidly solidified on a cooling drum to obtain a laminated unstretched film. At this time, the thickness of each layer was controlled by adjusting the extrusion amount of each material. Next, after longitudinal stretching (3.4 times) at 85 ℃, the temperature is further increased to 95
After transverse stretching at ℃, heat setting at 210 ℃, film thickness 90μm
A biaxially stretched film of was obtained.

The support S-4 was prepared in the same manner as S-3 except that the film thickness ratio of the three layers was S-2: S-1: S-2 = 1: 2: 3.

Support S-5 (preparation method for PEN) 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and 2 parts by weight of TINUVIN P326 (manufactured by Ciba Geigy) as an ultraviolet absorber are dried by a conventional method. After melting, the film was melted at 300 ° C., extruded from a T-die, and longitudinally stretched 3.3 times at 140 ° C., and then laterally stretched 3.3 times at 130 ° C. Furthermore, 250
The film was heat set at 6 ° C. for 6 seconds to obtain a film having a thickness of 90 μm.

<Preparation of Photosensitive Material> In the same manner as in Example 1, an undercoat layer and a photographic constituent layer were provided on one side of each support. However, in the support S-4, an undercoat layer and a photographic constituent layer were provided on the side where the layer thickness of S-2 was thin.

Further, conductive layers B-1 and B-3 were provided on the other side of the support in the same manner as in Example 1.

Further, a corona discharge of 8 W / (m ² · min) was applied on the conductive layers B-1 and B-3 to apply the following coating solution M.
C-1 was applied to give a dry film thickness of 1 μm.

<MC-1> Nitrocellulose 35 parts by weight Polyurethane resin 35 parts by weight Lauric acid 1 part by weight Oleic acid 1 part by weight Butyl stearate 1 part by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co Deposition γ -Fe ₂ O ₃ (long axis 0.2 μm, short axis 0.02 μm, Hc = 650 oersted 5 parts by weight Further, on the coating layer of MC-1, the following coating solution OC-2
Was applied at 10 ml / m ² .

<OC-2> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml Thus, a multilayer color photographic light-sensitive material having a magnetic recording layer was prepared.

Each of the prepared samples was cut as shown in FIG. 1 and packed in a cartridge to prepare a film having a width of 35 mm and 24 shots. This was loaded into a photographic camera with a magnetic head described in U.S. Pat. No. 5,021,820, and magnetic information was recorded on tracks C0 to C3 (see FIG. 1) by the signal input method described in the specification in the same manner as in the specification.

This film was subjected to the same developing treatment as in Example 1 and then applied to a magnetic recording / reproducing apparatus to examine a reproduction output error. The reproduction output error is a case where the average reproduction output per track is 70% or less of the reproduction output when the magnetic head accurately contacts the film.

Further, the obtained photographic light-sensitive material was subjected to JISK
Perforated as described in 7519-1982. The perforation strength was measured using this photographic light-sensitive material.

Orientec Tensilon RT
The end portion 3 of the perforation strength measuring jig shown in FIG. 2 is grasped by the A-100 with a tensilon chuck. Length 250mm
The perforation part of the film is sprocket part 1
Inset, through the film, 100g at film edge 2
Hang the weight. The other film end 4 was gripped by a chuck and pulled at a speed of 40 mm / min, and the maximum load when the perforation part broke was defined as the perforation strength.

In addition, the curl recovery property was measured by the following method.

A film having a sample size of 12 cm × 35 mm is wound around a core having a diameter of 10 mm so that the emulsion surface is inwardly wound, and the film is heated at 55 ° C. for 20 minutes.
It is treated for 3 days under the condition of% RH, and is wound. After that, it is released from the core, immersed in pure water at 38 ° C. for 15 minutes, and then dried with a hot air dryer at 55 ° C. for 3 minutes while applying a load of 50 g. The load was removed, the sample was suspended vertically, the distance between both ends of the sample was determined, and it was evaluated how much the original distance was restored to 12 cm. The evaluation was performed according to the following criteria.

⊚: 70% or more ◯: 60% or more and less than 70% Δ: 50% or more and less than 60% x: less than 50% Further, the same as in Example 1 was examined. The results are shown in Table 5.
Shown in.

[0187]

[Table 5]

From Table 5, it can be seen that by using the present invention, the photographic light-sensitive material having the magnetic recording layer has excellent performance in which magnetic recording input and output errors do not occur. It is considered that this is due to the reduction of dust adhesion due to the excellent conductivity, and the improvement of the film adhesion and the film peeling.

Example 5 A support S-2 was prepared in the same manner as in Example 1.

8 W / (m ² · min) on both sides of the prepared support
Corona discharge treatment, and coating solution B-1 or B-4 is applied to one side of the support so that the dry film thickness is 0.6 μm to form conductive layer B-1 or B-4. Further, a corona discharge of 8 W / (m ² · min) is applied on the conductive layer B-1 or B-4, and the undercoating coating solution A-2 is applied to the undercoating layer A so that the dry film thickness becomes 0.1 μm. -2 was formed.

On the other surface of the support, an undercoat layer coating solution B-
10 is applied so that the dry film thickness is 0.6 μm, and the undercoat layer B-
10 was formed, and in the same manner as in Example 1, a coating layer OC-1 was formed on the undercoat layer B-10.

<Coating Liquid B-10> After water dispersion of Lx-1 (solid content 30% by weight) 270 g Compound (UL-1) 0.6 g Finish with water 1000 ml Further, in the same manner as in Example 1, the undercoat layer A was used. -2 was provided with a photographic constituent layer. In the same manner as in Example 1, dust adhesion, film formation, and haze on the photographic constituent layer side were measured. The results are shown in Table 6.

[0193]

[Table 6]

From Table 6, no influence on the photographic performance was observed by providing the conductive layer on the photographic constituent layer side.

Example 6 <Preparation of support> A support TAC was prepared in the same manner as in Example 2.
(Film thickness 110 μm, elastic modulus 410 kg / mm ² ) S-1 (film thickness 90, 8
0, 70 μm, elastic modulus 575 kg / mm ² ), S-4 (film thickness 90, 80,
70 μm, elastic modulus 450 kg / mm ² ), S-5 (film thickness 90, 80, 70
μm, elastic modulus 725 kg / mm ² ) was prepared.

<Preparation of Photosensitive Material> In the same manner as in Example 4, a conductive layer B-1 was provided on each of the prepared supports in the same manner as in Example 4. Furthermore, MC-
1, OC-2 was applied.

An undercoat layer was coated on the other side of the support, and a photographic constituent layer was further provided. The heat treatment shown in Table 7 was applied before OC-2 was coated and before the photographic constituent layers were coated. The heat treatment was carried out by winding the undercoat layer on the winding core having a diameter of 30 cm. The number of reproduction output errors, the perforation strength, and the film attachment property of the obtained sample were examined and the results are shown in Table 7.

[0198]

[Table 7]

From Table 7, supports S-1, S-4 and S-5
Even if the film thickness is reduced to 70 μm, the TAC film thickness is 110 μm.
It can be seen that it has a perforation strength equal to or higher than that of It is also found that the heat treatment improves the film-forming property.

[0200]

According to the present invention, there is provided a silver halide photographic light-sensitive material excellent in charging property, film-forming property and transparency, and particularly excellent in charging property after development processing, and further having sufficient mechanical strength. It has a magnetic recording layer in which the adhesion between the magnetic recording layer and the magnetic head is sufficiently maintained, the occurrence of errors during reproduction of magnetic signals is reduced, and the reliability of magnetic recording is improved. It was possible to provide a silver halide photographic light-sensitive material.

[Brief description of drawings]

FIG. 1 is a plan view of a light-sensitive material of the present invention.

FIG. 2 is a perspective view showing a schematic configuration of a testing machine used for measuring the perforation strength of the light-sensitive material of the present invention.

[Explanation of symbols]

1 Sprocket part 2 Film edge 3 Tester end (chuck grip) 4 Film edge (chuck grip) 101 perforation C0 to C3 tracks (record magnetic information) F00 to F29 tracks (record magnetic information)

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-295016 (JP, A) JP-A-6-301152 (JP, A) JP-A-4-125547 (JP, A) JP-A-4- 208937 (JP, A) JP-A-4-151244 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/85 G03C 1/795 G03C 1/04 501

Claims (6)

(57) [Claims] 1. A photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, and having a layer containing a latex having a sulfonic acid group on at least one side of the support, And, the conductive metal oxide particles in the latex-containing layer , having the sulfonic acid group
The volume fraction of latex is 5% or more and 50% or less.
A silver halide photographic light-sensitive material, characterized in that it is contained in a box . 2. The silver halide photograph according to claim 1, wherein the amount of the sulfonic acid group contained in the latex having the sulfonic acid group is 0.5 to 10 wt% with respect to the binder of the latex layer. Photosensitive material. 3. Having at least one magnetic recording layer
A silver halide copy according to claim 1 or 2,
True photosensitive material. 4. The support comprises a polyester layer,
The reester layer is used as a copolymerization component for the metal sulfonate group.
Aromatic dicarboxylic acid and / or polyalkyl having
Lenglycols and / or saturated aliphatic dicarboxylic acids
Characterized by using a photographic support containing an acid
The silver halide photographic feeling according to claim 1, 2 or 3.
Light material. 5. A polyester film having a multilayer structure.
Copolymerized with at least one layer of the polyester film
As a component, an aromatic dicarlic group having a metal sulfonate group
Boric acid and / or polyalkylene glycols, and
And / or saturated aliphatic dicarboxylic acid
A true support is used.
The silver halide photographic light-sensitive material according to item 3. 6. A naphthalene dicarb as a photographic support.
Polyester mainly composed of acid and ethylene glycol
Characterized by using a polyester film consisting of
4. A silver halide photographic light-sensitive material according to claim 1, 2 or 3.
material.