JP2655199B2 - Silver halide photographic material - Google Patents

Description

The present invention has a transparent magnetic layer (or a magnetic recording layer), has excellent adhesiveness before and after a development process, can collect a base, and has environmental pollution. The present invention relates to a silver halide photographic light-sensitive material having no silver halide (hereinafter referred to as a photographic light-sensitive material or a photographic light-sensitive material).

(Prior art) Conventional silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials)
It is almost impossible to input various kinds of information (for example, shooting date, weather, enlargement ratio, number of prints, etc.) at the time of shooting with a camera, and can only slightly input the shooting date optically.

Further, even at the time of printing, it is impossible to input information to the photosensitive material itself, which is a major obstacle to high-speed processing and cost reduction.

Inputting various types of information to the photosensitive material is a very important means for improving the operability and simplifying the camera in the future. The magnetic recording method as the information input means,
It is important because it can be input and output arbitrarily and is inexpensive, and has been studied in the past.

For example, by appropriate selection of the amount and size of the magnetizable particles contained in the magnetic recording layer, the magnetic recording layer having the transparency required for the photographic material at the time of shooting and having no adverse effect on the granularity can be made transparent. The provision on the back surface of a light-sensitive material having a suitable support is described in U.S. Patent Nos. 378294, 4279945, 4302523 and the like. Further, a signal input method to the magnetic recording layer is disclosed in, for example, International Publication Nos. 90-4205 and 90-04212.

Various information, which has been conventionally difficult, can be incorporated into the photosensitive material depending on the provision of the magnetic recording layer and the input / output method. For example, the date and time of shooting, weather, lighting conditions, reduction / enlargement ratio, etc. The conditions, the number of reprints, the location to be zoomed, the development of messages and the like, and the printing conditions can now be input and output to the magnetic layer of the photosensitive material.

Furthermore, the present invention has the potential of being applied as a signal input / output means when an image is output directly from a photographic material to a television / video image.

However, these magnetic recording layers are generally prepared by dispersing and coating a ferromagnetic substance in the form of fine particles in a binder. The binder used at this time is preferably vinyl chloride, vinyl acetate, or polyurethane, which is generally used for video tape recorders. Certainly, by dispersing the magnetic fine particles in these binders and applying them to the back layer of the photographic material to provide the magnetic recording layer, excellent adhesiveness and magnetic recording characteristics can be simultaneously satisfied.

On the other hand, in recent years, industrial waste discharged as a result of people's production activities has caused environmental pollution and has become a major social problem. As a countermeasure, it has been practiced to recover and reuse the base from photographic light-sensitive materials generated in the manufacturing or processing steps and to reduce the cost.

Therefore, using the magnetic recording layer of the photographic material as the binder used in the conventional video tape as it is,
It is impossible to easily remove the magnetic layer from the base of the photographic material, and the photographic material is handled as industrial waste as it is, resulting in environmental pollution and cost increase.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a photographic material having a transparent and excellent magnetic recording layer without impairing photographic performance. A second object of the present invention is to provide a photographic light-sensitive material which has excellent adhesiveness before and after the development processing and can easily recover the base.

(Means for Solving the Problems) An object of the present invention is to provide a photographic material having a photosensitive silver halide emulsion layer on at least one side of a support, wherein at least one side of the photographic material is transparent. A magnetic layer, and the coercive force thereof is 400 Oe or more, and the binder of the transparent magnetic layer or the binder of at least one layer closer to the support than the transparent magnetic layer is at least one of an acid, an alkali and a biodegradable binder. This has been achieved by a photographic light-sensitive material characterized by comprising one kind.

The present invention relates to a binder of the transparent magnetic layer itself for removing the transparent magnetic layer from the support, or a layer existing on the side of the support relative to the transparent magnetic layer (for example, an intermediate layer, an antistatic layer, an undercoat layer, etc.). Is easily removed with an acid, alkali or biodegradable binder, and the effect of the present invention is obtained by releasing and removing the magnetic layer from the support.

 Hereinafter, the present invention will be described in detail.

First, the magnetic material used for the transparent magnetic material of the present invention will be described.

The ferromagnetic fine powder used in the transparent magnetic layer of the present invention includes ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder, and ferromagnetic alloy powder. And barium ferrite can be used.

Examples of the ferromagnetic alloy powder include a metal content of 75 wt% or more and a metal content of 80 wt% or more of at least one 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, Rh, Pd, Ag, Sn, Sb, B, Ba, Ta, W, Re, A
u, Hg, Pd, P, La, Ce, Pr, Nd, Te, Bi, etc.). Further, the ferromagnetic metal component may contain a small amount of water, hydroxide, or oxide.

Methods for producing these ferromagnetic powders are known, and the ferromagnetic powder used in the present invention can also be produced according to a known method.

The shape and size of the ferromagnetic powder can be widely used without any particular limitation. The shape may be any of a needle shape, a rice grain shape, a spherical shape, a cubic shape, a plate shape and the like, but a needle shape and a plate shape are preferable in terms of electromagnetic conversion characteristics. The crystallite size and non-surface area are not particularly limited, but the crystallite size is preferably 400 ° or less, and the SBET is preferably 20 m ² / g or less, particularly preferably 30 m ² / g or more. Ferromagnetic powder
The pH and the surface treatment can be used without any particular limitation (the surface may be treated with a substance containing an element such as titanium, silicon, or aluminum, or a carboxylic acid, a sulfonic acid, a sulfate, a phosphonate, a phosphate, a benzoate, or the like). (It may be treated with an organic compound such as an adsorbent compound having a nitrogen-containing heterocycle such as triazole). The preferred pH range is 5
Will be ~ 10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / 3-valent iron. These magnetic recording layers are described in JP-A-47-32812.
No. 53-109604.

The content of the ferromagnetic fine powder per 1 m ^{2 of the} transparent support is 4
× 10 ^{-4 to 3} g, preferably 10 ^{-3 to 1} g, more preferably 4 ×
10 ^-3 to 4 × 10 ^-1 g.

Next, the acid / alkali or biodegradable binder used in the present invention will be described.

First, as an acid or alkali-decomposable binder, its solubility is sharply improved by treatment under acidic or alkaline conditions (generally an aqueous solution or a water-miscible organic solvent) for a long time (1 hour or more), and the binder is released from the support. Things or acidic,
Alternatively, there is no particular limitation as long as it is chemically decomposed under alkaline conditions and released from the support.

Among these binders, preferred are cellulose derivatives (monoacetyl cellulose, diacetyl cellulose, propionyl cellulose, hydroxyethyl cellulose, methyl cellulose, etc.), poly (meth) acrylates (for example, hydroxyalkyl- or allyl groups as ester residues). (Eg, hydroxyethyl, hydroxyethylphenyl), carboxyalkyl- or allyl group (eg, carboxyethyl, carboxyphenyl), aminoalkyl- or allyl group (eg, aminoethyl, aminoethylphenyl, etc.), poly (meth) acrylamide (For example, poly (N, N-dihydroxyethylacrylamide)).

Next, preferred as biodegradable binders are poly (β-hydroxyalkanoate), polycaprolactone, starch, starch-containing polymers (polyethylene,
Polypropylene) and the like, and more preferred are poly (3-hydroxybutyrate), poly (3-hydroxybutyrate), a polymer mainly composed of poly (4-hydroxybutyrate), starch-containing polyethylene, and starch-containing It is polypropylene.

These are biodegradable plastics-Overseas trend research report-(published by the Bioindustry Association, June 1989)
Month).

When the support is recovered by removing the magnetic layer comprising the acid-alkali or the biodegradable binder of the present invention or the binder layer forming one layer on the support side from the photographic material, the solubility or decomposition of the binder is reduced. In order to promote the property, it is preferable that the photographic material is finely cut in advance,
It is preferable that the treatment bath for further decomposition is appropriately heated, stirred, or blown with air. At this time, when processing a photographic material having an acid, an alkali or a biodegradable binder, it is general to use a processing solution, but the solvent used is not particularly limited, and for example, water, alcohol (methanol, ethanol, Propanol) and ketones (acetone, methyl ethyl ketone, acetophenone, etc.) are preferred, and a mixed solvent thereof may be used.

As the compound imparting acidity and alkalinity used in the present invention, preferably, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia And alkali compounds such as hydrochloric acid, sulfuric acid, sodium hydroxide and potassium hydroxide.

Further, a method of decomposing a light-sensitive material using a biodegradable binder will be described.

In the present invention, the recovered photographic material is firstly cut into small pieces, and if there is a gelatin emulsion, it is treated with a gelatin-decomposing enzyme (for example, amylase) to remove the gelatin emulsion layer. It is preferred to decompose in water. The activated sludge used at this time is not particularly limited, and for example, standard activated sludge of the Chemical Inspection Association of Japan (CBC) can be used.

These can be further decomposed by blowing air and maintaining the temperature at 20-35 ° C. The longer the time required to decompose the biodegradable polymer of the present invention by the above method, the better, but in the present invention, from the viewpoint of recovery efficiency, it is from half a day to 20 days, more preferably from 1 day to 7 days.

In the magnetic layer comprising the acid, alkali or biodegradable binder of the present invention or a constituent layer closer to the support than the magnetic layer, a crosslinking agent may be added, for example, epoxy-based, isocyanate-based, silane-coupled crosslinking. Agents can be used.

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

The magnetic recording layer of the present invention is preferably provided on the back surface of the photosensitive material. The magnetic recording layer can be provided on the back surface of the transparent support by coating or printing. Further, a solution of the decomposable polymer of the present invention in which magnetized particles are dispersed and a solution of a polymer for forming a transparent support (for example, triacetyl cellulose) are co-cast to prepare a transparent support having a magnetic recording layer. In this case, it is preferred that the compositions of the two polymers be substantially the same.

Improve lubricity, curl control, antistatic,
A function such as adhesion prevention may be provided, or these functions may be provided by providing another functional layer. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve the scratch resistance.

The rear surface of the transparent support having the magnetic recording layer can be calendered to improve smoothness and improve the S / N ratio of a magnetic signal. In this case, it is preferable to apply a photosensitive layer on the transparent support after calendering.

Examples of the method of applying the magnetic recording layer on a support include air doctor coating, blade coating, air knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating,
Kiss coats, cast coats, spray coats, etc. can be used, and other methods are also possible. Specific descriptions of these methods are described in detail in “Coating Engineering” published by Asakura Shoten, pages 253 to 277 (published by Showa 46.3.20). Have been.

According to such a method, the magnetic layer coated on the support is subjected to a treatment for orienting the magnetic powder in the layer while necessary if necessary, and then the formed magnetic layer is dried.
The conveying speed of the support at this time is usually set at 10 m / min to 500 m / min, and the drying temperature is controlled at 20 ° C. to 120 ° C.
Further, the magnetic recording medium of the present invention is manufactured by performing a surface smoothing process if necessary. These are, for example,
No. 23625, Japanese Patent Publication No. 39-28368, U.S. Pat.
No. 960, etc. In addition, Japanese Patent Publication No. 41-131
The method described in Publication No. 81 is fundamental in this field,
And it is considered an important technology.

In order to reduce errors in input / output signals of the magnetic recording layer of the present invention, it is preferable to include a slip agent in the outermost layer of the magnetic recording layer.

These slip agents are not particularly limited, but those which do not deteriorate photographic properties and cause no trouble in the production process are preferable.

These slip agents are disclosed in U.S. Pat.Nos. 4,275,146 and 3,933,5
No. 16, JP-B-58-33541, U.S. Patent No. 927,446, JP-A-55-126238, JP-A-58-90633, and JP-A-52-129520.

Preferred examples of the slip agent are described below, but the invention is not limited thereto.

Compound example S-3 C ₁₅ H ₃₁ COOC ₁₆ H ₃₃ S-4 (n) C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ (n) S-5 (n) C ₂₇ H ₅₅ COOC ₅₀ H ₁₀₁ (n) S-6 (iso ) C ₁₇ H ₃₅ COOC ₃₄ H ₆₉ (iso) S-7 (iso) C ₁₇ H ₃₅ COOC ₄₀ H ₈₁ (n) _{S-9 (iso) C 27} H 55 COOCH 2 4 OCOC 27 H 55 (iso) S-10 erucamide _{S-11 C 33 H 67 COOH} S-12 liquid paraffin Furthermore, the present invention, the hermetic adhesion improvement It is preferable to include a so-called matting agent in the outermost layer of the magnetic material layer,
The particle size is preferably from 1 to 3 μm. If the particle size is too large, an error in the magnetic properties tends to occur, and if it is too small, the adhesion resistance is poor.

By including these matting agents, the average height of the projections on the surface on the side of the magnetic layer is preferably 0.8 to 3.0 μm. These matting agents are disclosed in JP-A-64-77052.
Nos. 62-14647, JP-B-48-5966, 39-11501
Nos. 46-1796, 47-18004, 55-33747, JP-A-53-7231, 60-153722, etc. preferable. The amount of the matting agent used in the present invention is preferably 5 to 300 mg / m ² , more preferably 10 to 300 mg / m ² .

Specific examples of the matting agent are described below, but the invention is not limited thereto.

M-4 CH ₂ -CH _{2 n} average particle size 2.4μm Hereinafter, other constituent factors of the present invention will be described.

The support of the light-sensitive material used in the present invention is not particularly limited, but various plastic films can be used, and preferred are cellulose derivatives (for example, triacetyl-, propionyl-, dataanoyl-, acetylpropionyl-acetate, etc.), Polyamide, US Patent No.
Polycarbonate described in 3,023,101, JP-B-48-40414
No. (for example, polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene, polysulfone, polyarylate, polyetherimide, etc.
Particularly preferred are triacetyl cellulose and polyethylene terephthalate.

These supports may be added with a plasticizer and used for the purpose of imparting flexibility. In the case of cellulose esters, plasticizer-containing substances such as triphenyl phosphate, biphenyl diphenyl phosphate, and dimethyl ethyl phosphate are usually used.

These supports vary depending on the polymer type, but the thickness is
From 1 mm sheet to 20 μm thin film, it can be used properly depending on the application, but is usually 50 μm to 300 μm
Is the thickness range.

The molecular weight of these support polymers is preferably 10,000 or more, more preferably 20,000 to 800,000.

The support may contain a dye for the purpose of neutralizing the base color, preventing light piping, preventing halation, and the like.

In order to firmly adhere a photographic layer (for example, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, a transparent magne layer or a conductive layer of the present invention) on these supports, chemical treatment, mechanical treatment, Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
After performing a surface activation treatment such as laser treatment, mixed acid treatment, ozone oxidation treatment, etc., the adhesive force may be obtained by directly applying a photographic emulsion, or once these surface treatments are performed, or without surface treatment. A method may be used in which an undercoat layer is provided and a photographic emulsion layer is coated thereon.

At that time, a single layer of a gelatin solution dispersed in a methylene chloride / ketone / alcohol mixed organic solvent is applied to the cellulose derivative to provide an undercoat layer.

Gelatin hardeners include chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), epichlorohydrin resins And the like. These undercoat liquids can contain various additives as necessary. Examples include surfactants, antistatic agents, dyes for coloring antihalation agents, pigments, coating aids, antifoggants and the like. When the undercoat liquid of the present invention is used, an etching agent such as resorcin, chloral hydrate, chlorophenol and the like can be contained in the undercoat liquid.

In the underlayer of the present invention, inorganic fine particles such as SiO ₂ and TiO ₂ or polymethyl methacrylate copolymer fine particles (1 to
10 μm) as a matting agent.

The undercoating liquid according to the present invention may be prepared by a well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or U.S. Pat.
It can be applied by an extrusion coating method using a hopper described in the specification of 1,294. U.S. Pat.Nos. 2,761,791, 3,508,947, 2,94
Two or more layers can be simultaneously coated by the method described in JP-A Nos. 1,898 and 3,526,528, "Coating Engineering", Yuji Harazaki, page 253 (published by Asakura Shoten in 1973).

The light-sensitive material of the present invention comprises a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer and the like, and these are mainly used in a hydrophilic colloid layer.

In that case, as a binder of the hydrophilic colloid layer,
For example, proteins such as gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, and poly Acrylic acid copolymer, polyacrylamide or a derivative and partial hydrodispersion thereof, dextran, polyvinyl acetate, polyacrylate,
A mixture of two or more of these colloids may be used, if necessary, such as rosin.

Among them, gelatin or a derivative thereof is most used, and the gelatin mentioned here refers to so-called lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin.

In the present invention, an anion, a nonion, a cation,
A betaine-containing fluorine-containing surfactant can be used in combination.

These fluorine-containing surfactants are described in JP-A-49-10722, British Patent No. 1,330,356, JP-A-53-84712 and JP-A-54-1422.
No. 4, No. 50-113221, U.S. Pat.No. 4,335,201, No. 4,34
No. 7,308, UK Patent No. 1,417,915, JP-B-52-26687
No. 57-26719, No. 59-38573, JP-A-55-149938
No. 54-48520, No. 54-14224, No. 58-200235,
Nos. 57-146248 and 58-196544, UK Patent No. 1,436,4
No. 02, etc.

 These preferred specific examples are described below.

I-1 C ₈ F ₁₇ SO ₃ K I-2 C ₇ F ₁₅ COONa In the present invention, a nonionic surfactant may be used.

Hereinafter, specific examples of the nonionic surfactant preferably used in the present invention will be shown.

Compound example N-1 C ₁₁ H ₂₃ COOCH ₂ CH ₂ O ₈ H N-3 C ₁₆ H ₃₃ OCH ₂ CH ₂ O ₁₂ H The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of a photographic light-sensitive material. For example, a surface protective layer, an emulsion layer,
Examples include an intermediate layer, an undercoat layer, and a back layer.

The amount of the fluorine-containing surfactant and the nonionic surfactant used in the present invention may be 0.0001 g to 1 g per square meter of the photographic light-sensitive material, and is more preferably 0.000 g to 1 g.
5 to 0.5 g, particularly preferred is 0.0005 g to 0.2 g. or,
Two or more of these surfactants of the present invention may be mixed.

Also, ethylene glycol, propylene glycol, 1,
A polyomal compound such as 1,1-trimethylolpropane as disclosed in JP-A-54-89626 can be added to the protective layer of the present invention or another layer.

Other known surfactants may be added alone or as a mixture to the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, sensitization and other improvements in photographic properties.

Also, in the present invention, lubricating compositions, for example, U.S. Pat.Nos. 3,079,837, 3,080,317, 3,545,970,
Modified silicones and the like described in JP-A-3,294,537 and JP-A-52-129520 can be contained in the photographic constituent layers. Further, higher fatty acid esters are also effective.

The photographic light-sensitive material of the present invention contains U.S. Pat.
Polymer latexes described in 411,911, 3,411,912 and JP-B-45-5331 can be included.

The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened by various organic or inorganic hardeners (alone or in combination).

In particular, color reversal films and color negative films can be mentioned as typical examples of preferred silver halide color photographic light-sensitive materials in the present invention. In particular, a color negative film for general use is a preferred color photographic light-sensitive material.

 Hereinafter, a general-purpose color negative film will be described.

The light-sensitive material of the present invention comprises at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support.
The number of layers and the order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as the layers are provided. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-light-sensitive layers such as intermediate layers of the respective layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, couplers described in the specification of No. 61-20038, DIR compounds and the like may be contained, and a color mixing inhibitor is used as usually used. May be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No., JP-A-57-112751, JP-A-62-200350, JP-A-62-2065
No. 41, No. 62-206543, No. 56-25738, No. 62-63936
No. 59-202464, Japanese Patent Publication No. 55-34932, No. 49-15495
It is described in the specification.

Silver halide grains have crystal defects such as those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, and twin planes. Or a composite form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparati
on and types) ”and No. 18716 (January 1979),
Page 648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemicet Phisique Photogra
phique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi)
c Emulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photo).
graphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1979); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The efficiency of the present invention is:
This is particularly noticeable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such a process are described in Research Disclosure Nos. 17643 and 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, Examples thereof include alcohols or phenols, aliphatic carboxylic esters, aniline derivatives, and hydrocarbons. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used.Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone,
Cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling speed T 1/2 is preferably 30 seconds or less. The film thickness means a film thickness measured under a humidity of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling speed T 1/2 can be measured according to a method known in the art. For example, A Green
(A. Green) et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 19
Vol. 2, No. 2, pp. 124-129, and can be measured by using a serometer (swelling meter). T 1/2 is reached when the color developer is processed at 30 ° C. for 3 minutes 15 seconds. The saturated film thickness is defined as 90% of the maximum swelled film thickness, and is defined as the time required to reach the film thickness of T 1/2.

The film swelling speed T1 / 2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is
150-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
The development can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. Nos. 3,342,597, 3,342,599, Schiff base compounds described in Research Disclosures 14,850 and 15,159, and 13,942 are described.

Next, as the photosensitive material of the present invention, a preferred form of the photosensitive material of the present invention is a roll-shaped film capable of easily inputting a signal to the transparent magnetic recording layer when the film is transported by a camera or a printer. In this roll-shaped film, the area of one frame of the image exposure unit is set to be 350 mm ² or more and 1200 mm ² or less, and the magnetic information recordable space is 15 mm of the area of one frame of the image exposure unit.
% Or more is preferable. Specifically, it is preferable to make the number of perforations per screen smaller than 135 formats. It is particularly preferred that the number of perforations per frame be four or less.

Information can also be optically entered into the magnetic information recordable space using an LED or other issuer. It is also preferable to input magnetic information and optical information in the space in an overlapping manner. The magnetic recording format is open to the world 90-0420
Preferably, the method disclosed in No. 5 is followed.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. Other cartridges proposed in the following patents can also be used. (Actual opening 58-67329
No., JP-A-58-181035, JP-A-58-182634, Shokai
No. 58-195236, U.S. Pat.No. 4,221,479, Japanese Patent Application No. 63-57785
Japanese Patent Application No. 63-183344, Japanese Patent Application No. 63-325638, Japanese Patent Application No. 1-21862, Japanese Patent Application No. 1-25622, Japanese Patent Application No. 1-30246
No., Japanese Patent Application No. 1-20222, Japanese Patent Application No. 1-21863, Japanese Patent Application No. 1
No. -37181, Japanese Patent Application No. 1-333108, Japanese Patent Application No. 1-85198,
Japanese Patent Application No. Hei 1-172595, Japanese Patent Application Hei 1-172594, Japanese Patent Application Hei 1
No. 172593, U.S. Pat. No. 4,846,418, U.S. Pat. No. 4,848,693, U.S. Pat. No. 4,732,275) Cartridges having means for controlling the attitude of the cartridge in the camera are particularly preferred. (Japanese Patent Application No. 1-214895
No.) Next, the cartridge used in the present invention contains a synthetic plastic as a main component.

In molding the plastic of the present invention, a plasticizer is mixed with the plastics as necessary. As the plasticizer, for example, trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone,
Representative examples include di-n-octyl succinate, bromonaphthalene, and butyl palmitate.

Specific examples of the plastic material used in the present invention are shown below, but are not limited thereto.

Specifically, polystyrene, polyethylene, polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, methyl methacryl resin, vinyl formal resin, There are vinyl butyral resin, polyethylene terephthalate, Teflon, nylon, phenol resin, melamine resin and the like.

Particularly preferred plastic materials for the present invention are polystyrene, polyethylene, polypropylene and the like.

Further, the cartridge of the present invention may contain various antistatic agents. Although the antistatic agent is not particularly limited, carbon black, metal oxide particles, nonions, anions,
A cation, a betaine-based surfactant, a nonion, an anion, a cation and a betaine polymer can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538.

Usually, the cartridge is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties.

Furthermore, the sphere may be of the current size, but the diameter of the current 25 m / m cartridge is not more than 22 m / m, preferably 20 m / m.
It is effective to reduce the size of the camera if it is less than m / m or more than 14 m / m. Further, in the current cartridge, the leading end of the spool on the side that engages with the film drive unit of the camera is protruding, which is an obstacle to miniaturization of the camera. Therefore, it is preferable to eliminate this portion. As a result, the volume of the cartridge, which is currently about 35 cm ³ , can be reduced. The cartridge case capacity is 30
cm ³ or less preferably it is preferable that the 25 cm ³ or less and more preferably 20 cm ³ or less. Weight of plastic used for cartridge and cartridge case is 1g or more 25
g or less, preferably 5 g or more and 15 g or less.

The ratio of the volume of the cartridge case to the plastic used for the cartridge and the cartridge case is 4
-0.7, preferably 3-1.

In the case of the cartridge incorporating the 135 color photosensitive material in the present invention, the total weight of the plastic used for the cartridge and the cartridge case is usually 1 g or more and 25 g or less,
Preferably it is 5 g or more and 15 g or less.

Next, the form of the cartridge incorporating the color photosensitive material described in the present invention will be described.

The form of the cartridge of the present invention is not particularly limited, but is preferably compatible with a commercially available camera. Furthermore, the present invention may be applied to a new camera compatible with a cartridge incorporating the color photographic material of the present invention. Examples of these specific cartridges are shown in FIG. 1 (the internal structure is further shown in FIGS. 2 to 4 and the magnetic track of the film is shown in FIG. 5).

(Examples) Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 1-1) Preparation of Base A dope solution and a cellulose triacetate dope solution each comprising the binder of Table 1 in which γ · Fe ₂ O ₃ (specific surface area: 25 m ² / g, manufactured by Pfizer Inc. (USA)) were dispersed were used. The film was cast to prepare a 122 μm thick film base having a 2 μm thick transparent magnetic recording layer. The coating amount of γ · Fe ₂ O ₃ was 0.14 g / m ² . Sample 1-1 (control) does not contain γ-Fe ₂ O ₃ .

This base was provided with a back layer having the following composition to provide a base for a photosensitive material. The surface having the magnetic recording layer was used as a back layer.

(Back layer composition) First layer cellulose triacetate 0.1 g / m ² ethylene glycol 0.08 g / m ² SnO ₂ / Sb ₂ O ₃ / SiO ₂ (weight ratio 90/10/1, average particle size 0.12 μm) 0.2 g / m ² Second layer Cellulose diacetate 0.32 g / m ² Aerosil 0.02 g / m ² Compound example S-4 0.01 g / m ² Compound example M-5 0.04 g / m ² It has been confirmed that the disclosed signal input method is possible.

1-2) Preparation of photosensitive material After performing a corona discharge treatment on the opposite side of the back layer of the undercoated cellulose triacetate film support, each layer having the following composition is applied in a multi-layered manner to obtain a multilayer color photosensitive material. Was prepared.

(Composition of photosensitive layer) A photosensitive layer was prepared in exactly the same manner as the photosensitive layer described in Example 1 of JP-A-2-93641.

(Processing of Sample) The sample was cut into a film having a width of 135 mm and having a format shown in FIG.

 The development of these samples was performed as follows.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fixed 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 05 seconds The processing solutions used for each process are as follows Was.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0 pH10.0 Bleach solution Ferric ammonium ethylenediaminetetraacetate 100.0g Disodium ethylenediaminetetraacetate 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0 pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0 pH6.6 Stabilizer Formalin (40%) 2.0ml Polyoxy Ethylene-p-monononyl phenyl ether (average degree of polymerization: 10) 0.3 g Water was added to 1.0. (1) Transmittance The unexposed sample was developed and fixed as described in (1). The light transmittance was measured. The sample 1-1 (control) was defined as 100, and the relative value thereof was shown in Table 1 as a relative transmittance.
The total light transmittance was measured according to ASTM D-1003.

(2) Adhesion After the completed sample was left in an atmosphere of 25 ° C. and 50% RH for 2 weeks, an adhesion test was performed by the following method. The surface tested here is the back side.

(A) Adhesion test method for dry film On the surface to be tested, make 7 cuts at intervals of 5 mm in the vertical direction to make 36 squares, and use an adhesive tape (for example, Nitto Electric Industry Co., Ltd.) , Nitto tape) and quickly peel it off in the 180 ° direction. In this method, the case where the unpeeled portion is 90% or more is class A, and the case where it is 60% or more is B.
Grade, less than 60% is C class. Adhesive strength sufficient for practical use as a photographic material is classified into Class A among the above three-grade evaluation. The test was performed on the back side.

(B) Adhesion test method for wet film At each stage of development fixing, washing with water, a scratch is made on the film in the processing solution by writing with a writing mark, and this is strongly rubbed with a fingertip five times. The adhesive strength was evaluated based on the maximum peeling width.

When the constituent layer does not peel off more than the scratch, it is class A, when the maximum peeling width is within 5 mm, it is class B, and the others are class C. Adhesive strength sufficient for practical use as a photographic material is classified into B or more, preferably A class, in the above three-grade evaluation. The evaluation was performed on the back side.

(3) Coercive force The coercive force was measured from the magnetic recording layer side.

(4) Evaluation of output error of magnetic recording According to the signal input method disclosed in the aforementioned WO 90-04205, a light-sensitive material magnetically input from the back side is subjected to 50
The output operation was performed 0 times, and the number of errors was shown. The output error of the photosensitive material which was subjected to development processing after magnetic input was also evaluated.

(5) Base recoverability After removing the emulsion layer side of the undeveloped photographic material with an aqueous solution of sodium nitrite, it is finely cut (1 mm × 1 mm) in a 0.1N hydrochloric acid aqueous solution or a 0.1N sodium hydroxide aqueous solution, or active. The mixture was allowed to stand in a sludge aqueous solution (by blowing air) at room temperature for 2 days with stirring. After thoroughly washing the treatment liquid with water, the obtained base is dried and a 1 mm thick base is prepared again,
The transmittance was measured.

A control sample without a magnetic layer was defined as a relative transmittance as 100% transmittance.

 The lower the transmittance, the worse the base recovery.

Comparative Compound A; Cellulose Triacetate B; Vinyl Chloride / Butyl Acetate Copolymer As can be seen from Table 1, samples 1-2 to 1-4 using the binder of the present invention have transmittance, adhesiveness, coercive force, and magnetic output. The error and the base recovery were excellent. On the other hand, Samples 1-5 to 1-10 using the comparative compound were significantly inferior in base recoverability.

From the above, it can be seen that the present invention is superior to the conventional technology.

Example 2 2-1) Preparation of Support A cellulose triacetate dope was cast to prepare a 105 μm thick film base.

The following back layer was provided on one side (back layer) of the base.

(A) Binder of the first layer Binder Listed in Table 2 (0.1 g / m ² ) SnO ₂ / Sb ₂ O ₃ / SiO ₂ particles (molar ratio 90/10/1, average particle size 0.12μ)
m) 0.2 g / m ² (b) Back 2nd layer Butyl acetate / vinyl chloride polymer (50/50) 2.5 g / m ² Cobalt-doped iron oxide fine powder (however, sample 2-1 (control) is cobalt-doped oxide) 0.20 g / m ² (c) Back 3rd layer Polymethyl methacrylate 0.32 g / m ² Aerosil 0.02 g / m ² Poly (methyl methacrylate / divinylstyrene) (molar ratio 95: 5) ( Average particle size 2.2 μm) 0.04 g / m ² C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ 0.005 g / m ² 2-2) Preparation of photosensitive material layer Prepared in 2-1) in exactly the same manner as in Example 1-2). A light-sensitive material layer was provided on the layer on the side of the support opposite to the back.

 The prepared sample was evaluated as shown in Table 2.

As can be seen from Table 2, Samples 2-2 to 2-4 of the present invention are satisfactory in all respects. On the other hand, Comparative Samples 2-5 to 2-10 were significantly inferior in base recoverability.

Example 3 A support was prepared in the same manner as in Example 2-1) except that the thickness of the cellulose triacetate was changed to 115 μm. Example 1 The reversal color emulsion layer described in Sample 101 was coated. However, the fluorine-containing surfactant used in Example 2 was added to the outermost layer (protective layer) of the emulsion layer in exactly the same manner.

The developing process used CR-56 process of color reversal process of Fuji Photo Film Co., Ltd.

Among the obtained samples 3-1 to 3-10, sample 3 of the present invention
-2 to 3-4 were excellent in all of permeability, adhesiveness, coercive force, magnetic properties and base recovery.

On the other hand, the comparative samples 3-5 to 3-10 could not satisfy the above performance in all respects.

[Brief description of the drawings]

FIG. 1 is a perspective view of a photographic film cartridge according to the present invention, FIG. 2 is a plan view showing a state of a leading end portion of the photographic film, FIG. 3 is a sectional view of the cartridge, and FIG. FIG. Fig. 5 ((5-
1) and (5-2)) are plan and sectional views of a magnetic recording track layer. [Explanation of Signs] 1 ... Photo film patrone 2 ... Spool 3 ... Photo film 4 ... Patrone body 5 ... Film drawer port 7 ... Perforation 8 ... Protrusion 9 ... Protrusion 10 ... Hole 11 Notch 12 Film passage 13 Step 14 Emulsion layer 15 Support 16 Transparent magnetic layer 17 Antistatic layer + scratch-resistant layer + lubricating layer 18 1 frame 19 perforation t-0 to t-1 magnetic recording tracks f00 to f29 magnetic recording tracks

Claims (3)

(57) [Claims] 1. A silver halide photographic material having a light-sensitive silver halide emulsion layer on at least one side of a support, wherein the photographic material has a transparent magnetic layer on at least one side thereof and has a coercive force of at least one side. Halogenation, wherein the binder is 400 Oe or more, and at least one binder of the transparent magnetic material layer or at least one layer closer to the support than the transparent magnetic material layer is made of at least one kind of acid, alkali or biodegradable binder. Silver photographic photosensitive material. 2. The silver halide photographic material according to claim 1, wherein the acid or alkali decomposable binder is a polymer having an ionic dissociating group or a derivative thereof. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the biodegradable binder is a polymer selected from a copolymer mainly composed of 3-hydroxyvalate and 4-hydroxybutyrate or a starch-containing polyethylene.