JPH0777776A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain silver halide photographic sensitive material reduced in static chargeability, superior in transparency, and good in adhesiveness by forming at least one magnetic recording layer and at least one layer having a specified compound. CONSTITUTION:The magnetic recording layer is formed by at least one and at least one layer contains at least one compound represented mainly by formula I or II in which each of R1 and R5 is H or lower alkyl; each of R2, R3, R4, and R6 is alkyl, aralkyl, or the like; D is a 5- or 6-membered heterocyclic ring containing 1 or 2 N; L1 is a divalent group; each of X. and X2 is an anion; each of x1, x2, y1, y2, z1, and z2 is a molar fraction and each of x1 and x2 is 0-20 %, each of y1 and y2 is 0-70 %, and each of z1 and z2 is 30-100%; A is a repeating unit having 2 copolymerizable ethylenically unsaturated groups and one of them on its side chain; and B is a repeating unit having a copolymerizable ethylenically unsaturated group.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a silver halide photographic light-sensitive material having a magnetic recording layer and excellent in transparency, adhesiveness and antistatic property, and transparency, adhesiveness, antistatic property and curl-eliminating property. And a silver halide photographic light-sensitive material excellent in

[0002]

2. Description of the Related Art For silver halide photographic light-sensitive materials, for example,
Type of photographic light-sensitive material, manufacturing number, maker name, emulsion No.
Various information related to photographic light-sensitive materials, such as shooting date / time, aperture, exposure time, lighting conditions, filters used, weather, size of shooting frame, model of camera, use of anamorphic lens, etc. Various information when shooting with the camera,
For example, various information necessary for printing such as the number of prints, filter selection, customer color preference, trimming frame size, etc., for example, number of prints, filter selection, customer color preference, trimming frame size. It is necessary to enter various information obtained at the time of printing, such as customer information, etc., from the viewpoint of management, improvement of print quality, and efficiency of print work.

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

Since the magnetic recording system is easy to record / reproduce, the use of the magnetic recording system for inputting the above various information to the photographic light-sensitive material has been studied and various techniques have been proposed.

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 photographing conditions. KAISHO 50-62627 publication, JP 49-4503 publication,
A transparent magnetic recording layer described in U.S. Pat. Nos. 3,243,376, 3,220,843, etc., and the necessary transparency is obtained on the back surface of the photographic light-sensitive material by selecting the amount of magnetizable particles and size. It is described in US Pat. Nos. 3,782,947, 4,279,945, and 4,302,523. Further, U.S. Pat.No. 4,947,196 and 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 the photographic film. ing.

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

On the other hand, in recent years, miniaturization of cameras has been desired. In order to achieve this, a means for further miniaturizing the cartridge (patrone) is most effective, and for this purpose, it is necessary to reduce the thickness of the support of the photographic light-sensitive material, By doing so, the mechanical strength of the support is lowered, and in some cases, damage such as breakage from the perforation portion occurs.

Since the polyethylene terephthalate film has a mechanical strength superior to that of cellulose triacetate, it is widely used as a support for photographic light-sensitive materials.

However, when a polyethylene terephthalate film is used as a support for a photographic light-sensitive material having a magnetic recording layer, when it is stored in a roll at a high temperature, a curl is formed, and the curl is eliminated by a developing process. However, there is a problem in that the contact with the magnetic head cannot be sufficiently maintained because of insufficient charge, and an error occurs during input and reproduction of a magnetic signal.

When a magnetic recording layer is provided on a support, in a photographic light-sensitive material provided with the magnetic recording layer, the magnetic head contacts the magnetic recording layer in the process of recording and reproducing information. Therefore, there is a problem that the photographic light-sensitive material is charged and an error occurs during reproduction of recording.

Further, there is a problem that the commercial value of photographic prints is impaired due to the attachment 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.

Among such conductive materials, Japanese Patent Laid-Open No. 56-1
It is known that the method using a crystalline metal oxide as described in Japanese Patent No. 43431 or the like is effective because its conductivity does not depend on humidity. However, since the crystalline metal oxide has a small crack, that is, a crack, in the layer containing it and impairs the transparency, or the layer containing it is brittle and easily broken, it is difficult to bond with the adjacent layer. It had the drawback of being inferior in sex.

[0014]

A first object of the present invention is to provide a silver halide photographic light-sensitive material having a magnetic recording layer in which the chargeability of the photographic light-sensitive material is reduced, and a silver halide in which the chargeability is reduced. To provide a photographic light-sensitive material.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having a magnetic recording layer having excellent transparency and good adhesiveness, and a silver halide photographic having excellent transparency and good adhesion. To provide a light-sensitive material.

A third object of the present invention is that it has sufficient mechanical strength, is excellent in eliminating curling, and has sufficient adhesion between the magnetic recording layer and the magnetic head even if environmental conditions change. A silver halide photographic light-sensitive material having a magnetic recording layer that is retained, reduces the occurrence of errors during magnetic signal input and reproduction, and has improved magnetic recording reliability, and silver halide that is excellent in curling curl. To provide a photographic light-sensitive material.

[0017]

The above object of the present invention can be achieved by any one of the following constitutions.

In a photographic light-sensitive material having a light-sensitive silver halide emulsion layer on one side of a support, it has at least one magnetic recording layer and the above-mentioned general formula [1] "Chemical formula 1"
[4] A silver halide photographic light-sensitive material having at least one layer containing at least one compound represented by "Chemical Formula 4".

The support is a polyester film,
The silver halide photographic light-sensitive material as described above, wherein the polyester contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid.

An aromatic dicarboxylic acid having a metal sulfonate group and at least one polyester layer formed by laminating two or more kinds of polyester layers having different supports as a copolymerization component and a polyalkylene glycol and / or a saturated fat. A silver halide photographic light-sensitive material as described above, which comprises a group-dicarboxylic acid.

The silver halide photographic light-sensitive material as described in (1) above, wherein the support comprises a naphthalene dicarboxylic acid and a polyester containing ethylene glycol as a main component.

In a photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, at least a compound represented by the above general formula [1] "Chemical formula 1" to [4] "Chemical formula 4" is used. At least one layer containing one kind,
Further, the support is a polyester film, and the polyester has a metal sulfonate group-containing aromatic dicarboxylic acid and a polyalkylene glycol as a copolymerization component and / or
Alternatively, a silver halide photographic light-sensitive material containing a saturated aliphatic dicarboxylic acid.

In a photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, at least a compound represented by the above general formula [1] "Chemical formula 1" to [4] "Chemical formula 4" is used. At least one layer containing one kind,
In addition, two or more types of polyester layers having different supports are laminated, and at least any one type of polyester layer is a polyalkylene glycol and / or saturated fat containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component. A silver halide photographic light-sensitive material containing a group dicarboxylic acid.

In a photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, at least one compound represented by the above general formulas [1] to [4] is used.
A silver halide photographic light-sensitive material, comprising at least one seed-containing layer, and the support comprising a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components.

The present invention will be specifically described below.

First, 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 powder, chromium dioxide magnetic powder, barium ferrite magnetic powder, etc. 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 magnetic metal 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-
Ni, Co-Fe-Ni, etc., and other components (Al, Si, S, Sc, Ti, V, Cr, Mn, Cu, Zn, Y, Mo, 20% by weight or less).
Rh, 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.

US Pat. No. 2,950,971 describes that a magnetic layer consisting of magnetic iron oxide dispersed in a binder is transparent to infrared radiation. US Pat.
No. 9,945 describes that when the particle size is reduced, the wavelength is increased even when the concentration of magnetic particles in the magnetic layer is relatively high.
It is described that the transmittance of 632.8 nm helium / neon laser light is improved.

However, when the magnetic recording layer is provided in the image forming region of the silver halide color photographic light-sensitive material, not only the red region but also the green region and the blue region must have high light transmittance.

In order to increase the light transmittance in the red region, the green region and the blue region, the particle size of the magnetic particles is reduced and the coating amount of the magnetic particles is also limited.

If the particle size of the magnetic particles is made smaller than a certain level, the required magnetic properties cannot be obtained. Therefore, it is preferable to make the particle size of the magnetic powder small within the range where the required magnetic characteristics are 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, other reactive resins and the like which have been conventionally used as binders for magnetic recording media are used. Mixtures of can be used.

As the above-mentioned thermoplastic resin, vinyl chloride-
Vinyl acetate copolymer, vinyl chloride resin, vinyl acetate and vinyl alcohol copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer,
Vinyl-based polymers or copolymers such as ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, nitrocellulose, cellulose acetate propionate, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or acrylic acid copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer Combined, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin,
Examples thereof include rubber resins such as polyether resins, polyamide resins, amino resins, styrene-butadiene resins, butadiene-acrylonitrile resins, silicone resins, and fluorine resins.

The above-mentioned thermoplastic resin has Tg of -40 to 150 ° C,
It is preferably 60 to 120 ° C., the weight average molecular weight is preferably 10,000 to 300,000, and more preferably the weight average molecular weight is 50,000 to 200,000.

The radiation-curable resin is a resin which is cured by radiation such as electron beam or ultraviolet ray, and examples thereof include maleic anhydride type, urethane acryl type, ether acryl type and epoxy acryl type.

Examples of thermosetting resins and other reactive resins include phenolic resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, and silicone-based curable resins.

The binders listed above may have a polar group in the molecule. Epoxy group as polar group, -CO
OM, -OH, -NR ₂ , -NR ₃ X, -SO ₃ M, -OSO ₃ M, -PO
₃ M ₂ and -OPO ₃ M (M is hydrogen, alkali metal or ammonium, X is an acid forming an amine salt, and R is hydrogen or an alkyl group).

A hydrophilic binder may also be used as the binder for the magnetic recording layer of the present invention.

The hydrophilic binder usable in the present invention is, for example, Research Disclosure No. 17643,
Water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters described on page 26, and No. 18716, page 651 can be mentioned.

As the water-soluble polymer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, acrylic acid type copolymer,
Examples include maleic anhydride copolymers, examples of cellulose ethers include carboxymethyl cellulose and hydroxyethyl cellulose, and examples of latex polymers include vinyl chloride-based copolymers, vinylidene chloride-based copolymers, acrylic ester-based copolymers. Examples of the latex include polymers, vinyl acetate-based copolymers, butadiene-based copolymers and the like. Of these, gelatin is the most preferable.

Gelatin may be unmodified or modified. In addition, some of them are colloidal albumin, casein, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids, for example,
It may be replaced with polyvinyl alcohol, poly N-vinylpyrrolidone, acrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates, gelatin derivatives and the like.

The hydrophilic binder containing gelatin is preferably hardened. Examples of hardeners that can be used include
Aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, US Patent number 3,
288,775, 2,732,303, British patent 97
Reactive halogen-containing compounds described in 4,723, 1,167,207 and the like, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,
3,5-triazine, U.S. Pat. No. 3,635,718, 3,2
32,763, British Patent 994,869, etc., compounds having a reactive olefin, N-hydroxymethylphthalimide, U.S. Pat. Nos. 2,732,316, 2,586,168, etc. N-
Methylol compound, isocyanates described in U.S. Pat.No. 3,103,437, U.S. Pat.No. 3,017,
280, 2,983,611 and other aziridine compounds, U.S. Pat.Nos. 2,725,294, 2,725,295 and other acid derivatives, U.S. Pat. Examples thereof include epoxy compounds and halogen carboxaldehydes such as mucochloric acid. Also,
It is also possible to use an inorganic hardener, and examples of the inorganic hardener include chrome alum and zirconium sulfate, and Japanese Patent Publication Nos. 56-12853 and 58-32699.
Belgian Patent No. 825,726, JP-A-60-225148, JP-A-51-126125, JP-B-58-50699, JP-A-5
The carboxyl group-activating type hardeners described in 2-54427, U.S. Pat. No. 3,321,313 and the like can also be mentioned.

Hardeners are typically 0.
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 binder is preferably used in an amount of 1 to 20 parts by weight based on 1 part by weight of the magnetic powder. More preferably, it is 2 to 15 parts by weight with respect to 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 a 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 perform multi-stripe coating, these coating heads may be arranged in multiple rows. Specific stripe coating methods include, for example, JP-A-48-25503, JP-A-48-25504, JP-A-48-98803, and JP-A-50-13803.
No. 7, No. 52-15533, No. 51-3208, No. 51-6
No. 239, No. 51-65606, No. 51-140703, No. 29-4221, US Pat. No. 3,062,181
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, preventing electrification, preventing adhesion, and improving friction / abrasive properties. Various additives such as agents 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. Abrasives can be added.

Examples of the lubricant include silicone oils such as polysiloxane, plastic fine powders such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, and fluorocarbons. These may be used alone or in combination. These may be added in an amount of 0.2 to 20 parts by weight with respect to 100 parts by weight of the binder.

Examples of the abrasive include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specifically, aluminum oxide (α-alumina, γ-alumina, corundum, etc.), chromium oxide ( Cr ₂ O ₃ ), iron oxide (α-Fe
₂ O ₃ ), oxides such as silicon dioxide and titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond. The average particle size of these is 0.05 to
1.0 μm is preferable, and it can be added in the range of 0.5 to 20 parts by weight with respect to 100 of the magnetic powder.

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

For imparting scratch resistance, a compound generally known as a slip agent can be used, but higher fatty acid esters are preferred. 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 various functions described above.

After providing the magnetic recording layer, calendering is performed on the layer to improve smoothness, and S of magnetic output is obtained.
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.

Next, the compounds represented by the general formulas [1] to [4] will be described.

[0063]

[Chemical 5]

[Wherein R ₁ represents a hydrogen atom or a lower alkyl group (preferably a methyl group or an ethyl group), and R ₂ ,
R ₃ and R ₄ are each an alkyl group (preferably having 1 carbon atom).
To 8 alkyl groups, cycloalkyl groups), preferably aralkyl groups (preferably benzyl groups), alkenyl groups, allyl groups. R ₂ , R ₃ and R ₄ may be the same or different. _{Two of} R ₂ , R ₃ and R ₄ may be connected to form a 5-membered ring or 6-membered ring together with the nitrogen atom.

L ₁ represents a divalent group. For example, an alkylene group having 1 to 6 carbon atoms, a phenylene group, an alkenylene group, an aralkylene group having 7 to 18 carbon atoms, -COO-Y-, -CONR ₇
It represents a group represented by -Y-. R ₇ represents an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms. Y represents 7 to 7 carbon atoms).
Represents 18 aralkylene groups. X ₁ represents an anion.
x ₁ , y ₁ and z ₁ represent a mole fraction, x ₁ is 0 to 20%, y ₁
Is 0 to 70% and z ₁ is 30 to 100%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain,
B represents a repeating unit having a copolymerizable ethylenically unsaturated group. ]

[0066]

[Chemical 6]

[In the formula, R ₅ represents a hydrogen atom or a lower alkyl group, and R ₆ represents an alkyl group, an alkenyl group, an aralkyl group or an allyl group. D is a 5- or 6-membered heterocyclic ring having one or two nitrogen atoms. D may have a substituent. X ₂ represents an anion. x ₂ ,
y ₂ and z ₂ represent a mole fraction, x ₂ is 0 to 20%, y ₂ is 0 to
70% and z ₂ are 30 to 100%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Indicates a unit. ]

[0068]

[Chemical 7]

[0069]

[Chemical 8]

[In the formula, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a lower alkyl group. L ₂ has an ionene chain 2
Represents a valent group, and L ₃ represents a monovalent group. A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a copolymerizable repeating unit having an ethylenically unsaturated group. Represent

X ₃ and x ₄ are 0 to 20 mol%, y ₃ and y ₄ are 0 to
70 mol% and z ₃ and z ₄ represent 30 to 100 mol%. ] L ₂ , L
The _3, the following general formula [5], [6], preferably contains at least one straight-chain represented by (7).

[0072]

[Chemical 9]

In the general formula [5], Z ₁ and Z ₂ represent an alkylene group having 1 to 7 carbon atoms, and R ₁₁ and R _{12 each} have 1 carbon atom.
Represents an alkyl group, an alkenyl group, a benzyl group, and an allyl group. Z ₁ , Z ₂ , R ₁₁ and R ₁₂ may have at least one substituent selected from an alkyl group, a cycloalkyl group, a hydroxyalkyl group and an alkenyl group.
R ₁₁ and R ₁₂ may combine to form a ring. W ₁ represents a divalent group. X ₃ represents an anion. n ₁ is an integer of ₁ to 100.

In the general formula [6], Z ₃ and Z ₄ are nitrogen 4
It represents an atomic group having 3 to 10 carbon atoms, which contains a primary cation and forms a ring. When an aromatic ring is formed by Z ₃ and Z ₄ , R ₁₃ and R
₁₄ is not needed. When Z ₃ and Z ₄ do not form an aromatic ring, R ₁₃ and R ₁₄ each represent an alkyl group, an alkenyl group or a benzyl group having 1 to 10 carbon atoms, and at least an alkyl group, a cycloalkyl group or a hydroxyalkyl group. It may have one substituent. Q ₁ and W ₂ represent a divalent group. Q
₁ represents an alkylene group, an alkenylene group or an aralkylene group. X ₄ represents an anion. n ₂ is an integer of 1 to 100, and a is 0 or 1.

In the general formula [7], R ₁₅ and R ₁₆ represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a hydroxyalkyl group, an alkenyl group, a benzyl group and an allyl group, and having 1 to 10 carbon atoms. At least 1 consisting of alkyl, cycloalkyl, hydroxyalkyl, alkenyl
It may have one substituent. X ₅ represents an anion. n ₃ is an integer of 1 to 100.

In the general formulas [5] to [7], W ₁ ,
As W ₂ and W ₃ , an alkylene group having 1 to 10 carbon atoms, an alkenylene group, and an aralkylene group are preferable. Two X ₃ , X ₄
May be the same or different.

Since actual n ₁ , n ₂ and n ₃ have distributions, the average values are shown in the preferable compound examples. The distribution width depends on the compound.

In the formula, A is divinylbenzene, 1,3-
Examples thereof include butylene diacrylate, diethylene glycol dimethacrylate, ethylene diacrylate, 1,6-hexane diacrylate, N, N'-methylenebisacrylamide, triethylene glycol diacrylate, ethylene glycol dimethacrylate and the like.

As B in the formula, olefins such as ethylene and butadiene, vinyl esters such as vinyl acetate, styrenes such as styrene and α-methylstyrene, acrylic acid esters such as ethyl acrylate and butyl acrylate, methyl methacrylate, Examples thereof include methacrylic acid esters such as butyl methacrylate, and acids such as itaconic acid, maleic acid, acrylic acid and methacrylic acid.

Two or more kinds of A and B may be used.

The method for producing the copolymer of the present invention is described in
60-51693, 58-56853, JP-A-62-9346, 55-67
The methods described in Nos. 746 and 55-65950 can be referred to.

The copolymer of the present invention (general formula [1],
Specific examples of [2]) are listed, but the invention is not limited thereto.

[0083]

[Chemical 10]

[0084]

[Chemical 11]

[0085]

[Chemical 12]

[0086]

[Chemical 13]

[0087]

[Chemical 14]

The copolymer of the present invention (general formula [3],
Specific examples of [4]) will be given.

[0089]

[Chemical 15]

[0090]

[Chemical 16]

[0091]

[Chemical 17]

[0092]

[Chemical 18]

[0093]

[Chemical 19]

[0094]

[Chemical 20]

[0095]

[Chemical 21]

These copolymers may be used alone, or may be applied in combination with other binders. Furthermore, curing agents can also be used with these binders.

The content of the copolymer of the present invention is preferably 0.
005-5 g / m ² , more preferably 0.01-3 g / m ^2.
m ² and more preferably 0.02 to 1 g / m ² . When a binder is used in combination, the weight ratio of the copolymer to the binder is preferably 99: 1 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70.

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 naphthalenedicarboxylic 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 elene glycol as main constituent components.

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, 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. Further, in the present invention, as the copolyester, a blended product of the above-mentioned copolyester and polyester can also be mentioned.

Examples of the dibasic acid include terephthalic acid, isophthalic acid and naphthalene dicarboxylic 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 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 the laminated film, and particularly preferably 0.
45 to 0.65 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, 4-sodium sulfo- Examples thereof include 2,6-naphthalenedicarboxylic acid or an ester-forming derivative represented by the following chemical formula 22, and compounds obtained by substituting these sodiums with other metals such as potassium and lithium.

[0108]

[Chemical formula 22]

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) As the polyalkylene glycols, the terminal —H of polyethylene glycol may be replaced with —CH ₂ COOR (R: H or an alkyl group 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 dimethyl adipate, dimethyl sebacate and the like which are esters of adipic acid and sebacic acid 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 the copolyester used in the present invention are both phosphoric acid, phosphorous acid and their esters and inorganic particles (silica, kaolin, calcium carbonate) in the polymerization stage. , Calcium phosphate, titanium dioxide, etc.), or the polymer after polymerization may be blended with inorganic particles. 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 the 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 this transesterification include acetates, fatty acid salts, carbonates and the like of metals such as manganese, calcium, zinc and cobalt. Among these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable. It is also effective to add a metal salt of a hydroxide or an aliphatic carboxylic acid, a quaternary ammonium salt or the like within a range that does not hinder the reaction or color the 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 one 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 having a single-layer structure of polyester layer-
-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% based on 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 stretched in the transverse direction. (B) A method in which an unstretched sheet is stretched in the transverse direction first and then in the longitudinal direction. (C) Unstretched sheet. A method in which the 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 stretching is performed to satisfy the mechanical strength, dimensional stability and the like of the photographic support. The area ratio is preferably 4 to 16 times. The heat setting can be performed in the temperature range of 150 to 240 ° C.

--Photographic Support Having Polyester Layer of Laminate Structure ---- When the film of the present invention has a laminate structure of two or more layers, the thickness of each layer is generally appropriate depending on the polyester and the 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 0.7 ≦ d ₅ / d ₄ ≦
3, more preferably 1 ≦ d ₅ / d ₄ ≦ 2, and the total thickness d ₄ of the polyester layer 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.

Even in the case where the polyester layer has a laminated structure of two or three layers, including a case where the laminated structure is two layers or three layers, the polyester layer having 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 photographic film, the photographic support has excellent insertability into the entrance of a splicer processor. Become a body.

The term "asymmetrical" as used herein means that they are physically, mechanically or chemically different. For example, the order in which the polyester layer, the copolyester layer or layers made of other materials are constituted, 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.

As a method for confirming the asymmetry of these laminated polyester layers, various analytical instruments can be used, and the layer constitution is not particularly limited, but the cross section of the film can be confirmed by microscopic observation. It can also be confirmed by taking a micrograph. Also, while observing this with a microscope,
Scrap each layer or cut it into halves, and scrape each layer from above and below to obtain the upper and lower layers or the analyte of each layer, and perform hydrolysis to measure with various measuring devices such as liquid chromatography and NMR. Alternatively, after the analyte is dissolved in a solvent, NMR analysis or GPC
(Gel Permeation Chromatography) analysis or intrinsic viscosity may be measured, or X-ray spectroscopic analysis of the substance to be analyzed may be performed directly on the powder, or IR may be obtained by mixing with KBr or the like.
(Infrared spectroscopic instrument) is analyzed, and as a result, the asymmetry of both outer layers can be confirmed or measured by the absolute amount or the position of the peak of the measurement result corresponding to the absolute amount, the difference in intensity, and 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 thereto. 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 Tg of glass transition temperature (Tg) of the polyester layer or the copolyester layer to Tg + 10.
It is biaxially stretched in the temperature range of 0 ° C. At this time, the above methods A, B, and C can be adopted in the same manner as the stretching method of the single-layer polyester layer. The stretching ratio is preferably in the range of 4 to 16 times in area ratio. Also, heat setting is 150 to 2
It can be performed in the temperature range of 40 ° C.

For the purpose of reducing the curling of the photographic support made of polyester, JP-A-51-16358 and JP-A-51-16358 have been used.
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.

Typical examples of the photographic light-sensitive material having a magnetic recording layer 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 grain contained in the silver halide photographic emulsion may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly in the inside of the grain.

The silver halide grains may have a regular crystal form such as a cube, octahedron or tetradecahedron,
It may have an irregular crystal shape such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and grains of various crystal forms may be mixed, but twin silver halide grains having two parallel twin planes facing each other are preferable. .

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the report Photographiesche Correspondents. (Photographishe Korrespondenz)
Volume 99, page 99, volume 100, page 57.

In the present invention, when tabular silver halide grains are used, the average value of the ratio of diameter to thickness of tabular grains (also referred to as aspect ratio) is preferably less than 5, but more preferably 1.1 or more and 4.5 or less. Less than 1, particularly preferably 1.
It is 2 or more and less than 4. This average value is obtained by averaging the ratio of diameter to thickness of all tabular grains.

The diameter of the silver halide grain is indicated by the diameter of the circle equivalent to the projected area of the silver halide grain (the diameter of the circle having the same projected area as the silver halide grain),
The thickness is preferably 5.0 μm, more preferably 0.2 to 4.0 μm, and particularly preferably 0.3 to 3.0 μm.

As the silver halide photographic emulsion, any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used, but a monodisperse emulsion is preferable.

Here, as the monodisperse silver halide emulsion,
It is preferable that the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more, more preferably 70% or more, and still more preferably the weight of all silver halide grains. 80% or more.

[0144] Here, the average particle diameter r, the particle size when the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is maximum
It is defined as ri (3 significant digits, rounding down to the minimum digit).

The grain size ri referred to here is the diameter of a silver halide grain when the projected image of the silver halide grain is converted into a circular image of the same area.

The particle size ri is, for example, 1 when the particles are observed with an electron microscope.
It can be obtained by enlarging the image by 10,000 to 70,000 times and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is indiscriminately 1,000 or more).

Particularly preferred highly monodisperse emulsions of the present invention are

[0148]

[Equation 1]

When the breadth of the distribution is defined by, the breadth of the distribution is 20% or less, more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

In the present invention, when silver iodobromide is used as the silver halide, the content of the silver iodide is 4 mol% or more and 15 mol or more as an average silver iodide content in the entire silver halide grains. % Or less, more preferably 5 mol% or more and 12 mol% or less, and particularly preferably 6 mol% or more and 10 mol% or less.

The silver halide grains contained in the silver halide photographic emulsion are preferably so-called core / shell type grains in which silver iodide is concentrated.

The core / shell type particle is a particle composed of a core that serves as a core and a shell that coats the core, and the shell is formed by one layer or more layers. The silver iodide contents of the core and the shell are preferably different from each other, and it is particularly preferable that the silver iodide contents of the core portions are maximized.

The silver iodide content of the above core is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more. The silver iodide content of the outermost shell of the above shells, that is, the shell which usually forms the outermost surface layer is preferably 5 mol% or less, more preferably 0 to 2 mol%. The proportion of the core is preferably 2 to 60% by volume of the entire particle, more preferably 5 to 50%.

The silver halide grains contained in the silver halide photographic emulsion are prepared by preliminarily allowing an aqueous solution containing a protective colloid and seed particles to be present in a reaction vessel, and supplying silver ions, halogen ions or silver halide fine particles as needed. It is obtained by crystal growth of seed particles. Here, the seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed grains is arbitrary and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred.

When seed grains are used for preparing a silver halide emulsion, the seed grains may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have a spherical or plate shape. It may have an irregular crystal form. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.
It is preferable to use the monodisperse spherical seed particles described in the specification of 2-408178.

The silver halide photographic emulsion can be produced by any of the acidic method, the neutral method and the ammonia method.

In the production of silver halide photographic emulsion,
The halide ion and the silver ion may be mixed at the same time, or the other may be mixed in the presence of either one. Also,
It may be grown by adding halide ions and silver ions successively or simultaneously while controlling the pH and pAg in the mixing vessel, while considering the critical growth rate of the silver halide crystal. The conversion method may be used to change the silver halide composition of the grains at any step of the silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel.

In the production of silver halide photographic emulsion,
A known silver halide solvent such as ammonia, thioether or thiourea can be present.

The silver halide grains contained in the silver halide photographic emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), in the process of forming grains and / or the process of growing grains. Rhodium salt (including complex salt)
And at least one selected from iron salts (including complex salts) can be used to add a metal ion so that these metal elements can be contained inside and / or on the surface of the particles, and the particles are placed in a suitable reducing atmosphere. By this, reduction sensitization nuclei can be imparted to the inside of the grain and / or the surface of the grain.

In the silver halide photographic emulsion, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may be contained. When removing the salts, Research Disclosure (Research D
isclosure (hereinafter abbreviated as RD)) 17643, Item II.

Conditions other than those mentioned above in the production of the silver halide photographic emulsion according to the present invention are described in JP-A-61-6643.
Gazette, gazette 61-14630 gazette, gazette 61-112142 gazette, gazette 62-
157024, 62-18556, 63-92942,
63-151618, 63-163451, 63-220238.
The optimum conditions can be selected with reference to known methods such as Japanese Patent Publication No. 63-311244 and Japanese Patent Publication No. 63-311244.

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 page 648-9 Supersensitizer page 996 IV-AE, J section 23-24 page 648-9 page Fogging agent page 998 VI page 24-25 page 649 stabilizer 998 page VI page 24-25 page 649 Page When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, 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 VII-I section 25 page 650 Dye image stabilizer page 1001 VII-J section 25 whitening agent 998 page V 24 page UV light Absorber page 1003 VIII-C, XIII-C page 25 to 26 Light absorber page 1003 VIII page 25 to 26 Light scattering agent page 1003 VIII Filter dye page 1003 VIII page 25 to 26 binder 1003 page IX 26 page 651 static Inhibitor 1006 page XIII 27 page 650 Hardener 1004 page X 26 page 651 Plasticizer page 1006 XII 27 page 650 Lubricant 1006 page XII 27 page 650 Activator and coating aid 1005 page XI 26-27 Page 650 matting agent page 1007 page XVI developer (included in light-sensitive 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 section 25 page VII-C to G magenta coupler page 1001 VII-D section 25 page VII-C to G cyan coupler 1001 page VII- Item D Page 25 Items VII-C to G Colored Coupler Page 1002 Item VII-G Item 25 Page VII-G Item DIR Coupler Page 1001 Item VII-F Item 25 Page VII-F BAR Coupler Page 1002 Item 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 photosensitive layer by the dispersion method described in RD308119 page 1007, item XIV.

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

In the case of constructing a color photographic light-sensitive material, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above RD308119 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 may be provided, or the support may be treated with a chemical,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment,
Surface activation treatment such as high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment, 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.

[0171]

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, S-1 commercially available polyethylene terephthalate (intrinsic viscosity) was used.
0.65) 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added to 100 parts by weight of S-2 dimethyl terephthalate and 64 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SI
P) ethylene glycol solution (concentration 35% by weight) 28 parts by weight (5 mol% / total ester bond), polyethylene glycol (abbreviation: REG) (number average molecular weight: 4,000) 11 parts by weight (8.5% by weight / reaction product) Total weight), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.13 part by weight, Irganox 1010 (CIBA-GEIGY as an antioxidant
(Made by the company) was added so that it might be 1 weight% with respect to the product polymer. Then gradually raise the temperature and reduce the pressure to 280 ° C, 0.5 mm
Polymerization was carried out with Hg to obtain a copolyester (intrinsic viscosity
0.55).

After vacuum drying each of S-1 and S-2 at 150 ° C., two of the three extruders were used for S-2.
Melt extruded at ℃, the film thickness ratio of the three layers, S-2: S-1: S
-2 = 1: 2: 3, the layers were joined in a T-die in a layered manner, and rapidly solidified in 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 ° C,
After transverse stretching (3.4 times) at a temperature of 95 ° C, heat setting was performed at 210 ° C to obtain a biaxially stretched film having a film thickness of 80 and 90 µm (Support S-3).

S-2 single-layer base 80, 90 μm (support S-) prepared by the same method with three extruders as one
2) and S-1 single layer base 70, 80, 90 μm (support S-
1) was prepared.

Further, commercially available polyethylene-2,6-naphthalate polymer was dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C. Horizontal stretching of 3.3 times at ℃, 250 ℃
Heat-fixed for 6 seconds at 70, 80, 90 μm thickness of support S-4
Got Furthermore, in comparison with cellulose triacetate (TA
C) 110 μm was prepared.

(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 the undercoating coating solution B-1 was applied to the outer thin layer of the copolyester layer of the support to give a dry film thickness of 0.8 μm. To form a subbing layer B-1, and the other surface of the support is coated with the following subbing coating solution B-2 to a dry film thickness of 0.8 μm. -2 was formed.

<Undercoating Coating Liquid B-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 B-2> 40% by weight butyl acrylate, 20% by weight styrene And 40% by weight glycidyl acrylate copolymer latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish with water 1000 ml 8 W / (m on layer B-1 and subbing layer B-2
² min. Of corona discharge, and on the undercoat layer B-1,
An undercoat layer B-3 is formed by applying the following undercoat coating solution B-3 to a dry film thickness of 0.1 μm.
The undercoating coating solution B-4 shown below was applied to a dry film thickness of 0.1 μm to form an undercoating layer B-4 having an antistatic function.

<Undercoating Coating Liquid B-3> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Water 1000 ml <Undercoating liquid B-4> Compound of the present invention (shown in Table 1) 10 g Methanol 600 ml Acetone 400 ml Diacetyl cellulose 5 g Further, 8 W / (m ² · min) on the undercoating layer B-4. The corona discharge was applied, and the following coating solution MC-1 was applied so as to have a dry film thickness of 2 μm.

<MC-1> 10 parts by weight of carnauba wax was dissolved by heating with 150 parts by weight of toluene, cooled, and then mixed with 75 parts by weight of cyclohexanone and 150 parts by weight of methyl ethyl ketone, and then nitrocellulose BTH-produced by Asahi Kasei Co., Ltd. 1/2: 1
00 parts by weight (solid content 70 wt%) and Co-deposited γ-Fe ₂ O ₃ (long axis: 0.
8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 oersted) (5 parts by weight) were added, and the mixture was mixed by a dissolver for 1 hour and then dispersed by a sand mill to obtain a dispersion liquid.

(Heat Treatment of Support) After the undercoat layer and the back layer were coated by the above method, heat treatment was carried out under the conditions shown in Table 1. All the heat treatments were carried out by winding the back layer inside the core having a diameter of 30 cm.

(Coating of Photosensitive Layer) Further, the undercoat layer B-3 is used.
A corona discharge of 25 W / (m ² · min) was applied on the above, and the following photographic constituent layers were sequentially formed to prepare a multilayer color photographic light-sensitive material. The total thickness of the photographic constituent layers shown below was 25 μm.

Unless otherwise stated, the quantities shown in the photographic constituent layers shown below are expressed in quantities per 1 m ² .

Further, silver halide and colloidal silver are shown in terms of silver.

<Photographic Constituent Layer> First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.15 g UV Absorber (UV-1) 0.20 g Colored Cyan Coupler (CC-1) 0.02 g High Boiling Solvent (Oil-1) ) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average particle size 0.3 μm) (Average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (Average particle size 0.4 μm) (Average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 3.2 × 10 ^-4 (mol / silver 1 mol) ) Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D -1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain) Diameter 0.7 μm) (Average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ (mol / Silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) ) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (Average particle size 0.4 μm) (Average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (Average particle size 0.3 μm) (Average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 010 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high sensitivity green sensitive emulsion layer (GH) Silver iodobromide Emulsion (average particle size 0.7 μm) (average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer; Layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g Ninth layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 µm) (average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 µm) (Average iodine content 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR Compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; high-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average particle size 0.8 [mu] m) (average iodide content of 8.5 mol%) 0.5 g sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of silver) sensitizing dye (S 11) 1.2 × 10 ^-4 (mol / mole of silver) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling solvent (Oil-2) 0.05 g Gelatin 1.0g 11th layer; first 1 Protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g Ultraviolet absorber (UV-1) 0.07 g Ultraviolet absorber (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1g High boiling point solvent (Oil-1) 0.07g High boiling point solvent (Oil-3) 0.07g Gelatin 0.8g 12th layer; 2nd protective layer (PRP-2) Compound A 0.04g Compound B 0.004 g Polymethylmethacrylate (average particle size 3 μm) 0.02 g Gelatin 0.7 g-Preparation of silver iodobromide emulsion-The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by the double jet method using monodisperse silver iodobromide grains having an average grain size of 0.33 μm (silver iodobromide content of 2 mol%) as seed crystals.

A solution (G-1) having the following composition was treated at a temperature of 70 ° C. and pA.
While maintaining g7.8 and pH 7.0, a seed emulsion corresponding to 0.34 mol was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, a solution (H-1) having the following composition and a solution (S-
1) and 1) were added over 86 minutes at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) while maintaining a flow rate ratio of 1: 1.

(Formation of External High Iodity Phase-Shell Phase-) Subsequently, while maintaining the pAg10.1 and pH6.0, (H-2) and (S
-2) and were added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them, and the pH is adjusted to 40 ° C.
And pAg were adjusted to 5.8 and 8.0, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a dispersion width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Solution Ocein gelatin 100.0 g 10% by weight solution of -1 of the following compound in ethanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml Compound-1: polyiso Propyleneoxy / polyethyleneoxy / sodium succinate <H-1> solution Ocein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> solution Silver nitrate 309.2g 28% ammonia Aqueous solution Equivalent to finish with water 1030.5 ml <H-2> solution Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml <S-2> solution Silver nitrate 1133.0 g 28% ammonia solution Equivalent to finish with water 3776.8 ml used other than the 10th layer For the silver iodobromide emulsion, the average grain size of seed crystal, temperature, pAg, pH, flow rate,
The emulsions having different average grain sizes and silver iodobromide contents were prepared by changing the addition time and the halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, 4-hydroxy-6-methyl-1.3,3a, 7-tetrazaindene, 1- Phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material further comprises the compound SU.
-1, SU-2, viscosity adjusting agent, hardener H-1, H-2,
Stabilizer ST-1, antifoggant AF-1, AF-2 (weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg /
m ² ) is contained.

(The structure of each compound used for preparing the sample is shown below.)

[0196]

[Chemical formula 23]

[0197]

[Chemical formula 24]

[0198]

[Chemical 25]

[0199]

[Chemical formula 26]

[0200]

[Chemical 27]

[0201]

[Chemical 28]

[0202]

[Chemical 29]

[0203]

[Chemical 30]

[0204]

[Chemical 31]

[0205]

[Chemical 32]

[0206]

[Chemical 33]

[0207]

[Chemical 34]

The photographic light-sensitive material obtained as described above was perforated as described in JIS K7519-1982.

Tensilon RTA-1 manufactured by Orientec Co., Ltd.
At 00, the end portion 3 of the perforation strength measuring jig shown in FIG. 2 is grasped by a tensilon chuck. A perforation part of a film having a length of 250 mm is fitted into the sprocket part 1, the film is passed through, and a 100 g weight is hung on the film end part 2. The other end 4 of the film 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.

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. The magnetic head described in U.S. Pat. No. 5,021,820 was loaded in a photographic camera, and signals were written on tracks C0 to C3 by the signal input method described in the specification.

In FIG. 1, 101 is perforation, and F00 to F29 are tracks for recording magnetic information like tracks C0 to C3.

After the development processing shown below was performed on this film. It was applied to a magnetic recording / reproducing apparatus and examined for reproduction output error. The reproduction output error means that the average reproduction output per track is free of electrostatic noise and is 70% or less of the reproduction output when the magnetic head accurately contacts the film.

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

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter (pH = 10.1) <bleaching liquid> Ethylenediaminetetraacetic acid iron (III ) Ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1 liter, and adjust to pH 6.0 with aqueous ammonia.

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

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

20 samples were tested for each sample, the reproduction output of all 24 frames was examined, and the number of films in which a reproduction output error occurred was counted.

The test environment in which signals were written in the camera was 25 ° C. and 50% RH. Also, the playback
It was carried out at 23 ° C. and 20% RH.

Also, one randomly selected film after development processing was printed at 23 ° C. and 20% RH for each sample for all 24 frames, and the number of dust visually observed on the print was determined. Measured.

Further, the haze of the back layer coating agent film before coating the photographic constituent layers on the emulsion side was measured according to JIS K-6714.

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 1 were obtained when the film-forming) 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 that 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.

Evaluation 5 4 3 2 1 Peeling condition None at all 0-20% 21-50% 51-100% 101% or more If the evaluation is 4 or more, it can be considered that the film formation 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 silver halide photographic light-sensitive material thus prepared was slit into a width of 35 mm, cut into 135 cm, and wound into a miniaturized cartridge (Patrone) having a cartridge body inner diameter of 18.5 mm and a spool inner diameter of 9 mm to reduce the size. The suitability was evaluated. Samples that could be involved in the full length are indicated by ◯, and samples that could not be included in the full length are indicated by Δ.

The above results are shown in Tables 1 and 2.

[0227]

[Table 1]

[0228]

[Table 2]

Comparative compound: Crystalline metal oxide A: SnO ₂ / Sb (9/1 weight ratio, average particle size)
0.2 μm) Nonionic surfactant B: C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₁₀ H Conductive polymer C:

[0230]

[Chemical 35]

From the results shown in Tables 1 and 2, when the compound of the present invention was used, the antistatic property was excellent even after the development processing, the reproduction output error did not occur, and the number of dusts on the print was extremely small. Furthermore, it has excellent transparency and film-forming property.

On the other hand, when the comparative compound A was used, the transparency was lost due to the formation of crack-like fine grains in the antistatic layer, and the film-forming property was poor, and when the comparative compounds B and C were used, It is understood that the antistatic property after development and the film forming property, particularly the wet film forming property, are poor.

Example 2 (Preparation of Photosensitive Material) Supports S-1 and S were prepared in the same manner as in Example 1.
-2, S-3, S-4 and TAC are coated with an undercoat layer B-2 and a conductive undercoat layer B-4 (conductive polymer: shown in Tables 3 and 4) in that order on the back layer side. In addition, the following coating liquid OC
-1 was applied at 10 ml / m ² .

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml Further, the undercoat layers B-1 and B-3 were coated on the other surface of the support and heat-treated under the conditions shown in Tables 3 and 4. . All the heat treatments were carried out by winding the back layer inside the core having a diameter of 30 cm.

Further, the photographic constituent layer of Example 1 was formed.

<Rewind property> Sample size 12 cm x
A 35 mm film is wound on a core having a diameter of 10 mm so that the emulsion surface is inwardly wound, and treated for 3 days under the conditions of 55 ° C. and 20% RH to give a curl. After that, release it from the core and use pure water at 38 ℃.
After soaking for 15 minutes, a load of 50 g is applied and drying is performed for 3 minutes in a hot air dryer at 55 ° C. The load was removed, the sample was hung 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 O: 60% or more and less than 70% Δ: 50% or more and less than 60% x: Less than 50% If the level is Δ or more, there is no practical problem.

Further, in the same manner as in Example 1 for each sample, the perforation strength, the number of dusts observed on the print, the haze of the back layer coating agent film, and the adhesion of various films were measured. The results are shown in Tables 3 and 4.

[0239]

[Table 3]

[0240]

[Table 4]

From the results shown in Tables 3 and 4, when the compound of the present invention was used together with the support of the present invention, the film was excellent in antistatic property even after the development treatment, the number of dusts on the print was small, and It can be seen that both strength and curl recovery are excellent.

On the other hand, even when the support of the present invention is used, when the comparative compound A is used, the transparency and the film-forming property are particularly poor,
When the comparative compound C is used, the antistatic property and the wet film forming property are particularly poor.

When a support other than the present invention is used,
It can be seen that the film-forming property is inferior, the number of dusts increases, and when the support is PET, the curl recovery property is inferior.

When the support S-4 is used, the film thickness is 70
It was found that even if the thickness was reduced to μm, the perforation strength was equal to or higher than that of TAC of 110 μm. It was also found that the heat treatment improves the film-attaching property and the curl recovery property.

[0245]

According to the present invention, firstly, a silver halide photographic light-sensitive material having a magnetic recording layer in which the chargeability of the photographic light-sensitive material is reduced, and a silver halide photographic light-sensitive material in which the chargeability is reduced are provided. can do.

Secondly, to provide a silver halide photographic light-sensitive material having a magnetic recording layer having excellent transparency and good adhesion, and a silver halide photographic light-sensitive material having excellent transparency and good adhesion. You can

Thirdly, it has a sufficient mechanical strength, the adhesion between the magnetic recording layer and the magnetic head is sufficiently maintained even when the environmental conditions change, and the magnetic signal is inputted and reproduced. It is possible to provide a silver halide photographic light-sensitive material having a magnetic recording layer in which the occurrence of errors is reduced and the reliability of magnetic recording is improved, and a silver halide photographic light-sensitive material having excellent curl-eliminating properties.

[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 end part 3 Tester end part (chuck grip part) 4 Film end part (chuck grip part) 101 Perforation C0 to C3 track (record magnetic information) F00 to F29 track (record magnetic information)

Claims (7)

[Claims] 1. A photographic light-sensitive material having a photosensitive silver halide emulsion layer on one side of a support, which has at least one magnetic recording layer and is represented by the following general formulas [1] to [4]. At least one layer having at least one compound
A silver halide photographic light-sensitive material having a layer. [Chemical 1] [Wherein R ₁ represents a hydrogen atom or a lower alkyl group (preferably a methyl group or an ethyl group), and R ₂ , R ₃ and R ₄ are each an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group). An alkyl group), preferably an aralkyl group (preferably a benzyl group), an alkenyl group or an allyl group. R ₂ , R ₃ and R ₄ may be the same or different. _{Two of} R ₂ , R ₃ and R ₄ may be connected to form a 5-membered ring or 6-membered ring together with the nitrogen atom. L ₁ represents a divalent group. For example, it represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, an alkenylene group, an aralkylene group having 7 to 18 carbon atoms, and a group represented by —COO—Y— and —CONR ₇ —Y—. R ₇ represents an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms). Y represents an aralkylene group having 7 to 18 carbon atoms. X ₁ represents an anion. x ₁ , y ₁ and z ₁ represent mole fractions, x ₁ is 0 to 20%, y ₁ is 0 to 70%, z ₁ is 30 to ₁
It is 00%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Indicates a unit. ] [Chemical 2] [In the formula, R ₅ represents a hydrogen atom or a lower alkyl group, and R ₆
Represents an alkyl group, an alkenyl group, an aralkyl group, and an allyl group. D is a 5- or 6-membered heterocyclic ring having one or two nitrogen atoms. D may have a substituent. X ₂ represents an anion. x ₂ , y ₂ and z ₂ represent mole fractions, x ₂ is 0 to 20%, y ₂ is 0 to 70%, and z ₂ is 30 to 100%.
%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Indicates a unit. ] [Chemical 3] [Chemical 4] [In the formula, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a lower alkyl group. L ₂ represents a divalent group having an ionene chain,
L ₃ represents a monovalent group. A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Represent x ₃ ,
x ₄ is 0 to 20 mol%, y ₃ and y ₄ are 0 to 70 mol%, z ₃ and z
₄ represents 30 to 100 mol%. ] 2. The support is a polyester film,
2. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester contains, as a copolymerization component, an aromatic dicarboxylic acid having a metal sulfonate group and a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid. material. 3. An aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and / or a polyalkylene glycol, and / or at least one polyester layer formed by laminating two or more polyester layers having different supports from each other. 2. A silver halide photographic light-sensitive material according to claim 1, which contains a saturated aliphatic dicarboxylic acid. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the support comprises a naphthalene dicarboxylic acid and a polyester containing ethylene glycol as a main component. 5. A photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, wherein at least one of the compounds represented by the above general formulas [1] to [4] is used.
An aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid, which has at least one seed-containing layer, and the support is a polyester film. A silver halide photographic light-sensitive material comprising: 6. A photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, wherein at least one compound represented by the above general formulas [1] to [4] is used.
Aromatic dicarbon having at least one seed-containing layer and laminating two or more polyester layers having different supports from each other, and at least any one of the polyester layers having a metal sulfonate group as a copolymerization component. A silver halide photographic light-sensitive material comprising an acid as a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid. 7. A photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, wherein at least one compound represented by the general formula [1] to [4] is used.
A silver halide photographic light-sensitive material, comprising at least one seed-containing layer, and the support comprising a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components.