JPH04124626A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photosensitive material having an excellent curling characteristic and adhesion resistance and the performance to prevent the deterioration in magnetic characteristics after development processing by providing silver halide photosensitive layers and hydrophilic binder layers having a specific swelling degree on the opposite side with a base in-between. CONSTITUTION:The silver halide photographic film having at least one layer of the transparent magnetic recording layers on the base is provided with the silver halide photosensitive layers and the hydrophilic binder layers on the opposite side. The hydrophilic binder may be the single layer thereof and may be used as the binder of the magnetic recording layer. The hydrophilic binder is exemplified by a water-soluble polymer, cellulose ester, latex polymer, water- soluble ester, etc. The adhesion resistance is enhanced and the input and output errors of magnetic recording are obviated by using the hydrophilic binder having <=200% swelling degree for the magnetic recording layers in particular.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of application of M soil) The present invention relates to a silver halide photosensitive material. More specifically, the present invention provides a photographic film having a magnetic recording layer using halogenated 1! between photosensitive materials.

(Prior art) Conventionally, silver halide photographic materials (hereinafter abbreviated as "sensitized materials") have been used to store various information at the time of camera photography (for example, date of photography, weather, etc.).
It was almost impossible to input information such as enlargement ratio, number of prints, etc., and it was only possible to input the shooting date optically. Even during printing, it is completely impossible to manually input information to the photosensitive material itself, which is a major obstacle to achieving high speed and cost reduction.

Inputting various types of information into the photosensitive material is a secretly important means for improving the operability and simplifying camera operations in the future. As a means for inputting information, magnetic recording methods are important because they allow arbitrary input/output and are inexpensive, and have been studied in the past.

By adding a magnetic recording layer to a sensitive material, it is now possible to embed various types of information into the material, which was previously difficult to do.
For example, it is possible to input and output information such as the date and time of shooting, weather, lighting conditions, conditions during shooting such as reduction/enlargement ratio, number of reprints, areas to be zoomed in, development of messages, etc., conditions during printing, etc. to the magnetic recording layer of the photosensitive material. It became so. Furthermore, TV/
It has the potential to be applied as a signal input/output means when directly outputting a video image from a photosensitive material to create an image.

Conventionally, two methods of applying a magnetic recording layer to a sensitive material have been considered: a method in which a magnetic recording layer is provided in a stripe pattern on the supinated surface of the photographic surface, as typified by motion picture film, and a method in which a transparent magnetic recording layer is provided over the entire surface. It has been.

The latter, a sensitive material having a transparent 8i recording layer, has the transparency required for a sensitive material at the time of photography by appropriately selecting the amount and size of magnetic particles contained in the magnetic recording layer 8N, for example. Further, a magnetic recording layer which does not adversely affect the granularity is provided on the back surface of a sensitive material having a transparent support. Specifically, US Pat. No. 378,294, US Pat.
It is described in No. 279945, No. 4302523, etc. Furthermore, a method for inputting signals to the magnetic recording layer is disclosed in Sekaimin No. 90-04205, No. 90-04212, and the like.

However, photographic materials having magnetic recording BN and a hydrophilic binder layer such as gelatin on one side curl due to atmospheric humidity during handling, and a certain degree of care was required in handling. Particularly when it is damp, it curls toward the hydrophilic binder layer, which deteriorates the flatness of the base in the camera and during printing, making it easy for problems such as out-of-focus and magnetic recording output errors to occur.

As a method for solving the above-mentioned gap H, it is known to provide the same hydrophilic binder on the back side.

Furthermore, in order to reduce costs, it has been considered to use a hydrophilic binder in the magnetic recording layer.

However, by providing a hydrophilic binder on the back surface, the drawback of easy adhesion in a film cartridge (patrone) has been overcome. Furthermore, when a hydrophilic binder is used as the binder in the magnetic recording layer, the aqueous binder layer swells during development, causing the problem that the magnetic material is likely to fall off or the orientation will be disturbed.

(Problems to be Solved by the Invention) The present invention provides a photographic film having a magnetic recording layer.
The object of the present invention is to provide a silver halide photosensitive material that has excellent curling properties, adhesion resistance, and prevents deterioration of magnetic properties after development.

(Means for Solving the Problems) In a silver halide photographic film having at least one magnetic recording layer on a support, at least a water-11 wettable layer is provided on the opposite side of the support from the silver halide photosensitive layer. This is achieved by a silver halide photographic light-sensitive material having one layer and having a degree of swelling of the water-swellable layer of 200% or less.

The hydrophilic binder of the present invention may be used as a single layer or as a binder for a magnetic recording layer.

The hydrophilic binder used in the present invention is described in Research Disclosure No. 17643.26 and Research Disclosure No. 18716.651,
Examples include water-soluble polymers, cellulose esters, latex polymers, and water-soluble polyesters. Examples of water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, and maleic anhydride copolymers, and examples of cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose. It is. Examples of latex polymers include vinyl chloride-containing copolymers, vinylidene anhydride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, and butadiene-containing copolymers. Among these, gelatin is most preferred. Further, gelatin derivatives and the like may be used in combination with gelatin.

As the gelatin, any of so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivatives, modified gelatin, etc. can be used, and among them, lime-treated gelatin and acid-treated gelatin are preferably used.

It is preferable to harden the magnetic recording layer containing gelatin so that the degree of swelling is 200% or less. Hardening agents that can be used in the magnetic recording layer are not particularly limited, but include formaldehyde, glutaraldehyde, etc. Aldehyde compounds, diacetyl, ketone compounds such as cyclopentanedione, bis(2-chloroethylurea), 2-
Hydroxy-4,6-dichloro-1,3,5-) riazine, etc. U.S. Pat. No. 3,288,775, U.S. Pat.
, 167.207, etc., divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5
-) Reazine, etc. U.S. Patent No. 3,635,718
No. 3. No. 232°763, British Patent No. 994,8
Compounds with reactive olefins, N-hydroxymethylphthalimide, and others described in U.S. Pat. No. 2,732,316 and U.S. Pat.
N-methylol compounds described in U.S. Pat. No. 68, etc., isocyanates described in U.S. Pat. No. 3,103,437, etc., U.S. Pat.
, U.S. Patent Nos. 2,725,294 and 2,725.
, 295, epoxy compounds described in US Pat. No. 3,091.537, and halogencarboxaldehydes such as mucochloric acid. Or, as a hardening agent for inorganic compounds, use chromium light pan, zirconium sulfate,
6-12853, 58-32699, Belky Patent No. 825,726, JP 60-225148, JP 51-126125, JP 58-50699, JP 52-54427, U.S. Pat. ,321,313
It is stated in the number etc. Examples include carboxyl group-activated hardeners.

Although it is preferable to use the above-mentioned hydrophilic binder as the binder of the magnetic recording layer used in the present invention from the viewpoint of cost reduction, when the hydrophilic layer is used as a single layer,
Known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, and mixtures thereof, which have been conventionally used as binders for magnetic recording media, can also be used.

The above resin has a Tg of -40°C to 150°C and a weight average molecular weight of 10,000 to 300,000, preferably 10,000 to 10,000.

Examples of the thermoplastic resin include vinyl chloride/vinyl acetate copolymer, vinyl chloride, vinyl acetate and vinyl alcohol,
Copolymers with maleic acid and/or acrylic acid, vinyl copolymers such as vinyl chloride/vinylidene chloride copolymers, vinyl chloride/acrylonitrile copolymers, ethylene/vinyl acetate copolymers, nitrocellulose, cellulose acetate Propionate, cellulose derivatives such as cellulose acetate butyrate resin, acrylic resin,
Rubber resins such as polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether 41 resin, polyamide resin, amino resin, styrene butadiene resin, butadiene acrylonitrile resin, silicone Examples include fluorine-based resins and fluorine-based resins.

Among these, vinyl chloride resin is preferred because it has high dispersibility of ferromagnetic fine powder.

Further, as the radiation-curable resin, a thermoplastic resin having a group having a carbon-carbon unsaturated bond bonded thereto as a radiation-curable functional group is used.

Preferred functional groups include acryloyl and methacryloyl groups.

In the bonding molecules listed above, polar groups (epoxy groups, C02
M, OH, NR2, NR3X, 503M, O
20sM,, P O3M2, OP O3M2, however, M
is hydrogen, an alkali metal or ammonium, and when there are multiple M's in one group, they may be different from each other. R is hydrogen or an alkyl group. ) may be introduced.

The polymer binders listed above may be used alone or in combination, and can be cured by adding a known isocyanate-based crosslinking agent and/or a radiation-curable vinyl monomer.

Examples of the ferromagnetic fine powder used in the magnetic recording layer of the present invention include ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic alloy powder, barium ferrite powder, etc. be.

An example of a ferromagnetic alloy powder is one in which the metal content is 75 wt$ or more, and the metal content of 80 wtX or more is at least one ferromagnetic metal or alloy (Fe, Co+Ni, Fe-C
.

, Fe-Ni, Co-Ni, Co-Fe-Xl, etc.), and other components (Al 1
51, S, Sc, T+, V, Cr, Mn, Cu +
Zn, Y+Mo, Rh, Pd+Ag, Sn, Sb,
B, Ba + Ta, W, Re, Au.

)1g, Pb, P, La, Ce, Pr, Nd+Te,
Bi, etc.) can be listed. 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 known methods.

The shape and size of the ferromagnetic powder are not particularly limited and can be widely used. The shape may be needle-like, rice-grain-like, spherical, cubic, plate-like, etc., but needle-like and plate-like shapes are preferable in terms of electromagnetic conversion characteristics. There are no particular restrictions on the crystallite size or specific surface area, but the crystallite size is 400. Below, 20m2/g with 5BET
The above is preferable, and the pH 1 surface treatment of the 0 ferromagnetic powder is particularly preferably 30 m2/g or more, and can be used without particular limitation. (The surface may be treated with a substance containing elements such as titanium, silicon, aluminum, etc., or carboxylic acid, sulfonic acid, sulfuric ester, phosphonic acid, phosphoric ester
The preferred pH range is from 5 to 1000 ferromagnetic iron oxide powder, which may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocycle such as benzotriazole. The iron/trivalent iron ratio is not particularly limited and can be used. Regarding these magnetic recording layers, Japanese Patent Application Laid-open Nos. 47-32812 and 53-109804
listed in the number.

The coating amount of the magnetic material may be as long as it has transparency to the extent that it does not cause any optical problems, and is preferably from 4.times.10@-' to 3 g, more preferably from 0.01 g to 0.2 g.

The magnetic recording layer of the present invention may further contain conventionally known lubricants and abrasives.

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

Examples of abrasives include non-magnetic inorganic powders with a Mohs hardness of 5 or more, preferably 6 or more, specifically aluminum oxides (α-alumina, γ-alumina, corundum, etc.), chromium oxides (Cr ), iron oxide (α-Fe
2e3), 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
~1.0 μm is preferable, and 0 to 100 ferromagnetic powder
．． It can be added in an amount of 5 to 20 parts by weight.

Further, it is desirable to use a matting agent, a slipping agent, etc. alone or in combination in the back layer of the present invention.

Sliding agents (S-1 to S-12) and matting agents (M-
Preferred specific examples of 1 to M-9) will be described, but the invention is not limited to these.

Compound example S-2 C.I.

C.B.

One stone 5i-O5i-0+vT (C)Ir)rcOcHzcHz)riHCHsC+s
Hff+COOC+Jff3 C15H31COOC4aHs+(n)(n)C*Js
sCOOCseH+*+(n)(iso)C+tH3s
COOC3J**(iso)(iso)C+JffsC
OOCnoHs+(n)COO-CzJxw(iso) (CIIzL Coo-CtJ4q(+30) S'- 9 -1O (iso)CzJssC00+CHz→i0cOcxt
llss(iso) erucic acid amide C. JitCOOH Liquid paraffin CI.

■ 1+CH. -C → TT COOCI(* Average particle size 2.1μm One←CH! -cn*-±" Average particle size 2.4μm Average particle size 2.5μm Average particle size 2.2μm Average particle size 2.2μm silica (spherical) (undefined form) Other constituent factors of the present invention will be described below.

The film support in the present invention is not particularly limited, but various plastic films can be used, and preferred ones include cellulose derivatives (for example, diacetyl-triacetyl-, propionyl-, butanoyl-
, acetylpropionyl acetate, etc.), polyamides, polycarbonates described in U.S. Pat.
1,4-cyclohexane dimethylene terephthalate, polyethylene 1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate, polyethylene naphthalate), polystyrene, polypropylene, polyethylene, polymethylpentene, These include polysulfone, polyethersulfone, polyarylate, polyetherimide, etc., and particularly preferred are triacetylcellulose and polyethylene terephthalate.

These supports are prepared by adding a laxative to them for the purpose of imparting flexibility, etc.
Sometimes used. Especially for cellulose esters,
Plasticizer-containing materials such as triphenyl phosphate, biphenyl diphenyl phosphate, dimethyl ethyl phosphate are commonly used.

These supports vary depending on the type of polymer, but the thickness is 1
Depending on the application, it can be used from a sheet of about 2.0 mm to a thin film of about 20 μm, but 60 μm is commonly used.
The thickness range is m-300 μm.

The molecular weight of these support polymers is preferably 10,000 or more, more preferably 20,000 to 80,000.

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

Chemical treatment, mechanical treatment,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
After surface activation treatment such as glow discharge treatment, activated plasma treatment, laser treatment, mixed acid treatment, or ozone oxidation treatment, it is possible to apply photographic emulsion directly to obtain adhesive strength, or to obtain adhesion after these surface treatments. After that, or without surface treatment, an undercoat layer may be provided and a photographic emulsion layer may be applied thereon.

For cellulose derivatives, a gelatin solution dispersed in a methylene chloride/ketone/alcohol mixed organic solvent is coated on a base layer to provide an undercoat layer.

As the gelatin hardening agent, the above-mentioned hardening agents can be used.

The undercoat liquid may contain various additives as necessary.1 For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifogging agents, etc.0 When using the undercoat liquid of the present invention, a processing/nching agent such as resorcinol, chloral hydrate, chlorophenol, etc. can also be included in the undercoat liquid.

The undercoat layer of the present invention may contain inorganic fine particles such as Sigh and Tilt or polymethyl methacrylate copolymer fine particles (1 to 10 μm) as a matting agent.

The undercoat liquid related to the present invention can be applied using generally well-known coating methods such as dip coating method, air knife coating method,
Curtain coat method, roller coat method, wire bar code method, gravure coat method, or U.S. Patent No. 2,88
Coating can be carried out by the extrusion coating method using a hopper as described in the specification of No. 1,294.

U.S. Pat. No. 2,761,791, 3, as appropriate.
608, No. 947, 2. 941. Two or more layers can be coated simultaneously by the method described in No. 898 and 3°526.528, Yuji M#, "Coating Engineering", p. 253 (published by Asakura Shoten, 1973).

The sensitive material of the present invention is composed of a silver halide emulsion layer, a magnetic recording layer, a back layer, a protective layer, an intermediate layer, an antihalation layer, etc., and these are mainly used in the wood-philic colloid layer.

In that case, binders for the hydrophilic colloid layer include, 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. Examples include polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives and partially hydrolyzed dispersions thereof, dextran, polyvinyl acetate, polyacrylic esters, rosin, and the like. A mixture of two or more of these colloids may be used if necessary.

Among these, gelatin or its derivatives are most used, and gelatin here refers to so-called lime-treated gelatin, acid-treated gelatin, and enzyme-treated gelatin.

In the present invention, anionic, nonionic, cationic, and betaine fluorine-containing surfactants can also be used in combination.

These fluorine-containing surfactants are disclosed in JP-A-49-10722.
No., British Patent No. 1,330,356, Japanese Unexamined Patent Publication No. 1983-8
No. 4712, No. 54-14224, No. 50-1132
No. 21, U.S. Patent No. 4,335.201, U.S. Patent No. 4,34
No. 7,308, British Patent No. 1,417,915, Japanese Patent Publication No. 52-26687, No. 57-26719, British Patent No. 59
-38573, JP-A-55-149938, JP-A No. 54
-48520, 54-14224, 58-20
No. 0235, No. 57-146248, No. 58-196
No. 544, British Patent No. 1,439°402, etc.

Preferred specific examples of these are described below.

1 1 CIFl'lSO3 1 2
CtF+5COONaCsF+tSOsN C
8! GOOKC,)l.

C,F+tSOtN+CHxCHCHzO±"10C
H! +rSOJaH c, n.

CaF+qSOxN+ CHxCHxO+"10 GHz
+rSOJaC@F1ffSOtNCHzCHxO-P
ONaNa CaFlqCH□C)IzOOCCHIC*lI+ y
ooc CH5OsNaCIFiffSO! NCHI
CHICI+! (OCRtCI+□)3NCH□COO
h CIF, SO, NCHtCH, N-CH3I CH3 Hs ■-11 C1@Ib+ CsF+tSOJ+ CHiCH* O÷ffH In the present invention, a nonionic surfactant may be used.

Specific examples of nonionic surfactants preferably used in the present invention are shown below.

Compound example C+ +HxsCOO+ CLCToOOsu'H: Iq
Hs 5cOO+C8zcLo +-r-+-C)It
-CH-CIl t-h+CHtCHzO juice HH C+ hHsscO+ CH@CIItO+rr H The layer to which the fluorine-containing surfactant and nonionic surfactant used in the present invention are added is particularly limited as long as it is at least one layer of the photographic material. For example, surface protective layer, emulsion layer,
Examples include an intermediate layer, an undercoat layer, and a back layer.

The amount of the fluorine-containing surfactant or nonionic surfactant used in the present invention may range from 0.0001 g to 1 g per square meter of the photographic material, and more preferably from 0.0005 g to 0.000 g per square meter of the photographic material. 5g, particularly preferably 0.0
005g to 0.2g. Moreover, two or more types of these surfactants of the present invention may be mixed.

Also, ethylene glycol, propylene glycol, 1
．． 1. 1-) Limethylolbroban, etc. JP-A-1984-
Polyomal compounds such as those shown in US Pat. No. 89,626 can be added to the protective layer or other layers of the present invention.

Other known surfactants may be added alone or in a mixture to the photographic constituent layer of the present invention. They are used as coating aids, but may also be used for other purposes, such as emulsification and dispersion. It is also applied to improve sensitization and other photographic properties.

In addition, in the present invention, lubricating compositions, such as those disclosed in US Pat. No. 3,079,837 and US Pat.
Same 3. 545. Modified silicones such as those disclosed in No. 970, No. 3, 284.537, and JP-A-52-129520 can be included in the photographic constituent layer. Furthermore, higher fatty acid esters are also effective.

The photographic light-sensitive material of the present invention has a photographic constituent layer in which U.S. Pat.
No. 411.911, 3. 411. 912, Japanese Patent Publication No. 45-5i331, etc., may 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 with various organic or inorganic hardening agents (singly or in combination). Typical examples include the aforementioned polymer hardeners and low molecular hardeners (HPI to HP8, H1 to H]7, etc.).

Representative examples of silver halide color photographic materials particularly preferred in the present invention include color reversal films and color negative films.

In particular, a general purpose color negative film is a preferred color photographic material.

The following description will be made using a general color negative film.

The light-sensitive material of the present invention has at least an I
There is no particular restriction on the number of silver halide emulsion layers and non-photosensitive layers and NIIm as long as N is provided.A typical example is to provide a support with substantially the same color sensitivity. However, it is a silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having different light sensitivities, and the light-sensitive layer can be used for any of exposure light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in order from the support side, such as a red-sensitive layer, a green-sensitive layer, and a green-sensitive layer. It is placed next to the sensitive color layer. However, depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer between each layer may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A-61-43748 and JP-A-59-]
No. 13438, No. 59-] No. 13440, No. 61-
20037 and 61-20038, etc., may be included, and a color mixing prevention layer as commonly used may be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are disclosed in West German Patent No. 1,121,470 or British Patent No. 9.
No. 23,045, JP-A-57-112751, JP-A No. 82
-200350, 62-206541, 62-
No. 206543, No. 56-25738, No. 62-63
No. 936, No. 59-202464, Special Publication No. 55-34
No. 932 and No. 49-154915.

Silver halide grains include those with regular crystals such as cubes, octahedrons, and dodecahedrons, those with irregular crystals such as spherical and plate shapes, and those with crystal defects such as twin planes. It can also be a combination of things or a combination of them.

The grain size of silver halide is approximately 0. It may be fine particles of 2 μm or less or large particles with a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No.

17643 (December 1978), pp. 22-23,”
■, Emulsion preparation (E++ulsion preparation)
ion and types)” and same No. 187
16 (November 1979), 648 pages, graphic "Physics and Chemistry of Photography", published by Paul Montell (P, G
lafkides, Chmicet Ph1sique
Photographique, Paul Mon
tel. +967), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (G, F, Duffin, Ph
otographic Emulsi.

n Chemistry (Focal Press,
+966no, "Production and Coating of Photographic Emulsion" by Zekman et al.
, Published by Focal Press (V, L, Zelikman
et at,, Making and Coatin
g Photographic Emulsion,
Focal Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3.655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Volume 248-257 (1970); U.S. Patent No. 4,4
34゜226, 4,414,310, 4,43
It can be easily adjusted by the methods described in No. 3.048, No. 4,439,520, British Patent No. 2,112,157, and the like.

The crystal structure may be --like, the interior and exterior may consist of different halide formations, it may be a layered structure, or silver halides of different compositions may be bonded by epitaxial bonding. Alternatively, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The efficiency of the present invention is particularly noticeable when emulsions sensitized with gold compounds and sulfur-containing compounds are used. Additives used in such processes are described in Research Disclosure No. 17643 and No. 18716, and the relevant sections 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 descriptions are shown in the table below.

Cervical chemical sensitizer 2 Sensitivity enhancer 3 Spectral sensitizer Super sensitizer 4 Brightener 5 Anti-fogging agent RD 17643 "L rule L" Page 23 Page 648 Right column Same as above Pages 23-24 Page 648 right column ~ Page 649 right column 24 pages 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, fluoride Page 25-26 Page 649 right column ~ Ilter dye, page 650 left column Ultraviolet absorber 7 Stin Inhibitor Page 25 Right column Page 650 Left to right column 8 Dye image stabilizer Page 25 9 Hardener Page 26 Page 651 Left column 1
0 Binder page 26 Same as above 11
Concave agent, lubricant Page 27 Page 650 Right column 12
fi fabric aid, pages 26-27, page 650, right column surfactant.In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the Research Disclosure +- (
RD) No. 17643, ■-C to G.

Examples of yellow couplers include US patent boxes 3 and 9.
33. No. 501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,248
, No. 961, Special Publication No. 58-10739, British Patent No. 1
．． No. 425,020, No. 1I 476.760, U.S. Patent Box 3. 973. No. 968, 4. 314. 0
No. 23, No. 4,511゜649, European Patent No. 249,
Preferred are those described in No. 473A and the like.

As magenta couplers, 5-pyrazolone and pyrazole azole compounds are preferred, and US Pat.
No. 10,619, No. 4,351°897, European Patent $
No. 73,636, U.S. Patent Box No. 3,061,432, U.S. Patent Box No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3
No. 3552, Research Disclosure No. 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Pat. No., WO(PCT)8B104
Particularly preferred are those described in No. 795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent Box 4°052.212.
No. 4. 146. No. 396, 4, 228.
No. 233, 4. 296. No. 200, 2,369
, No. 929, No. 2,801,171, No. 2. 772
．． No. 162, 2. 895. No. 826, 3.
772. No. 002, No. 3,758゜308, No. 4.
334. No. 001, No. 4.327.173, West German Patent Publication No. 3. 329. No. 729, European Patent No. 12
No. 1,365A, No. 249°453A, U.S. Patent Box 3
, No. 446,622, No. 4,333,999, No. 4,
No. 753,871, 4,451. No. 559, 4.
427. No. 767, 4,690. Preferred are those described in No. 889, No. 4,254°212, No. 4,296,199, and JP-A-61-42658.

The colored coupler for correcting unnecessary absorption of the color chart is Research Disclosure No. 17843.
Paragraph ■-G, U.S. Patent Box 41] 63.870, Japanese Patent Publication No. 57-39413, U.S. Patent Box 4,004,929, 4. 338. No. 258, British Patent 1!1.14
6,368 is preferred.

Couplers with excessively diffusive color patches include U.S. Patent No. 4,388,237 and British Patent No. 2,125.
, No. 570, European Patent No. 96,570, West Unique 1'F
(Publication) No. 3,234,533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
Same 4. 367, 282, 4.409.320, 4,576.910, British Patent 2,102,17
It is stated in issue 3 etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention.

The DIR coupler releasing the development inhibitor is the RD1 described above.
7643, the patent described in section ■-F, JP-A-57-1
No. 51944, No. 57-154234, No. 60-18
No. 4248, No. 63-37346, U.S. Patent Box 4, 2
48,962 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
Those described in JP-A No. 2,131,188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include U.S. Patent Box 4. 130. Competitive couplers described in U.S. Pat. No. 4,283,472, et al. 338. No. 393, 4.310,618
Long equivalent coupler described in JP-A-60-1859, etc.
DIR described in No. 50, JP-A No. 62-24252, etc.
a redox compound releasing coupler, a DIR coupler releasing coupler, a DIR coupler releasing redox compound, or
DIR redox releasing redox compound, European patent No. 1
No. 73,302A, a cystic release coupler that restores color after detachment, R, D, No. 11449, No. 2
No. 4241, bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Pat. No. 4,553,477
Gantt emitting coupler described in JP-A No. 1983-
Examples thereof include couplers that emit leuco color patches as described in No. 75747.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322.027 and the like.

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

The process and effects of latex dispersion methods and specific examples of latex for application are described in U.S. Pat. No. 4,199°363 and OLS No. 2. 541゜274 and 2,
No. 541,230, etc.

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 28 μm or less, and the film 11
It is preferable that the wetting speed T1/2 is 30 seconds or less. The film thickness is 25
℃ refers to the film thickness measured at a relative temperature of 55% (2 days), and the film swelling rate T1/2 can be measured according to methods known in the art. Photographic Science and Engineering (Pho Green) et al.
togr, ScI.

Eng.), Vol. 19, No. 2, pp. 124-129. T1/2 can be measured by using a swellometer (swelling membrane) of the type described in Eng.), Vol. 19, No. 2, pp. 124-129. 90% of the maximum swollen film thickness reached at this time is defined as the saturated film thickness, and is defined as the time it takes to reach this T1/2 film thickness.

The film swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions during coating. Further, the swelling rate is preferably 150 to 400%.

The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swelling i!4 film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, pages 28-29, and same No. 1871
The development process can be carried out by the usual method described in 6-615 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 processing. For this purpose, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,5
Indoaniline compound No. 97, No. 3,342,59
No. 7, Schiff base-type compounds described in Research Disclosure No. 14,850 and Research Disclosure No. 15゜159, Research Disclosure No. 13
, No. 924.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these.

Example 1 1-1 Creation of base On a cellulose triacetate paste with a thickness of 122 μm that has been prime-coated on both sides, the following first layer of back layer and second layer in which a magnetic material is dispersed are sequentially provided to form a film base l-^. Obtained. Note that the surface having the magnetic recording layer was defined as the back surface.

(Back layer 1st layer) Gelatin 5g/*2 1.2-bis(vinylsulfonylacetamido)ethane 0.48g/m2 (Back layer 2nd layer)
F') 7-Fe202 (specific surface area 25 m2/g manufactured by Pfizer Inc.) 0.1 g/a+2 Butyl acetate/vinyl chloride copolymer 2 g/I12 In addition, the above-mentioned back Nv, hardening agent used in the - layer 1.2 −
film base except that the amount of bis(vinylsulfonylacetamido)ethane) was 0.06 g/111']-
Film base I-8 was created in the same manner as A.

Further, a film base 1-C was prepared in the same manner as film base I-A except that the first back layer was omitted.

1-2 JP-A-2-93641 on the photosensitive material vlI film base prepared above
Each layer having the composition described in Example 1 of No. 1 was coated with heavy N to prepare a sample as a multilayer color photosensitive material.

1-3 Processing of Sample The sample was cut into a 24-shot film with a width of 351,111 mm.

These samples were developed as follows.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixation 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stable 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid y1 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide
1.4g potassium iodide
1.3 g hydroxylamine sulfate
2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.
Add 5 g of water and make 1.0 pH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water te 1.0p)l 6.
0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4,08 thioml
! Add ammonium aqueous solution (70ml 175.0ml sodium bisulfite 4.6g water)
1.0 pH 6.6 Stable liquid formalin (401) 2. On
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g Added water: 1.0 Next, the evaluation of these samples will be described.

(1) Measurement of back thickness Distilled water at 25° C. was poured onto the back side, and the change in thickness after 3 minutes was measured by swelling degree.

(2) Adhesion resistance test Place the sample before and after development into a regular film cartridge.
The sheets were stored in a number of 4 sheets and left for 2 days at a temperature and humidity of 40° C. and 80% RH, and their adhesion was evaluated. The evaluation was based on the surface area of the image being 300, and the area in close contact was expressed as a percentage.

(3) Curl Measurement The curl measurement of the light-sensitive material was evaluated by the commonly used type 1 curl. Measurements were performed at 25°C and 30%.

(4) Evaluation of magnetic output errors Using the signal manual method disclosed in the above-mentioned World Publication No. 90-04205, after magnetic input from the back side, the sensitive material was outputted 1000 times with a magnetic head, and the number of errors was calculated. Indicated.

Note that this output error was evaluated for the sensitive material that had been subjected to magnetic input and then developed.

The temperature and humidity in the evaluation were 25° C. and 30% RH.

The evaluation results are shown in Table 1.

As can be seen from Table 1, according to the present invention, a photosensitive material with good curling characteristics and good adhesion resistance was obtained.

Example 2 2-1 Creation of base A first back layer in which a magnetic material having the composition shown below was dispersed was formed on a triacetate cellulose paste with a thickness of 115 μm that had been prime-coated on both sides, followed by a second back layer. 2-
I got an A.

(First back layer) Gelatin 5g/a2 1.2-bis(vinylsulfonylacetamido)ethane 0.48g/m2r-Fe20
2 (specific surface area 25m2/g manufactured by Pfizer) 0.1g#
+2 M-5 (matting agent described in the specification) 0.04z/m2 (back layer 2nd N) S-4 (sliding agent described in the specification) 0.02g/■2 Also, the back layer The amount of hardening agent (l, 2-bis(vinylsulfonylacetamido)ethane) used was 0.06
Film base 2-8 was prepared in the same manner as film base 2-A except that g/■2 was used.

The preparation, processing, and evaluation of the photosensitive material were carried out in the same manner as in Example 1.

The results are shown in Table 2.

As seen from Table 2, the #moisture content of the magnetic recording layer is 200%.
Adhesion resistance and magnetic output error were particularly improved by using the following hydrophilic binder.

Example 3 Film base 2-A prepared in Example 2 was coated with JP-A-2-
The reversal color emulsion layer described in No. 854 Example 1, Sample 101 was coated. For the development process, CR-56 process of Fuji Photo Film ■Photographic film color reversal process was used.

Sample 3-1 of the present invention has excellent curling properties and adhesion resistance,
There were few magnetic output errors.

Claims (6)

[Claims] (1) A silver halide photographic film having at least one transparent magnetic recording layer on a support, having at least one hydrophilic binder layer on the side opposite to the silver halide photosensitive layer, and Swelling degree is 200%
A silver halide photographic material characterized by the following: (2) The silver halide photographic material according to claim 1, characterized in that the magnetic recording layer has at least one layer on the side opposite to the silver halide photosensitive layer. (3) The silver halide photographic material according to claim 2, wherein the magnetic recording layer is made of a hydrophilic binder, and the degree of swelling of the hydrophilic binder layer is 200% or less. (4) The silver halide photographic material according to any one of claims 1 to 3, wherein the silver halide photographic material is a color photographic material. (5) 5 to 300 m of matting agent with an average particle size of 1 to 3 μm
The silver halide photographic material according to any one of claims 1 to 4, which contains g/m_2 on the back side and has a surface roughness of 0.8 to 3.0. (6) The silver halide photographic material according to claim 5, which contains a slip agent and a fluorine-containing surfactant.