JPH05323484A - Silver halide photographic sensitive material having magnetic recording element - Google Patents

Abstract

PURPOSE:To obtain a laminated silver halide photographic sensitive material drastically improved in magnetic output, excellent in the adhesive strength of a magnetic recording layer and high in mechanical strength by laminating a supporting body by the use of polyester film layer containing a ferromagnetic fine powder and a polyester film layer containing no ferromagnetic fine powder. CONSTITUTION:In the silver halide photographic sensitive material containing the ferromagnetic fine powder in the transparent supporting body, the supporting body is laminated by a polyester film layer A containing the ferromagnetic fine powder and a polyester film B containing no ferromagnetic fine powder. Furthermore, by using a polyester having hydrophilic group or a polyester made of polyester terephthalate mixed with a material having absorptivity for water in at least one of the polyester film A or B, the silver halide photographic sensitive material more smaller in magnetic output error is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material containing a magnetic recording layer exhibiting excellent magnetic recording and reproducing characteristics.

[0002]

2. Description of the Related Art Conventionally, in a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material), as a means for recording information other than an image at the time of taking a picture or printing, one or more pieces outside the picture-taking screen are used. It is known that the magnetic recording medium has an elongated strip portion, but the presence of the strip portion causes uneven bending, and an air trap in the space between the strip portions adversely affects photographic properties. There were various drawbacks such as appearing. On the other hand, in order to make up for such a drawback, there is known one in which a transparent magnetic recording layer is provided in a photographing screen, as disclosed in US Pat. Nos. 3,782,947 and 4,279,945, and the world patent 90- Four
No. 205, No. 90-04212, etc., the signal input / output method, etc., photographing conditions such as date and time of photographing, weather, reduction / enlargement ratio, number of reprints, zoomed portion, message development, printing It is now possible to input the conditions of the time into the sensitive material and output to video equipment such as TV / video. However, when a magnetic recording layer is provided in the screen, it is necessary to minimize the content of the ferromagnetic fine powder in order to suppress the influence of the absorption of the ferromagnetic fine powder on the deterioration of the photographic sensitivity as much as possible. There is a problem in that the magnetic output characteristics become insufficient when the content of Fe is reduced, and it is necessary to use the smallest possible amount of ferromagnetic fine powder to exert the maximum magnetic characteristics. On the other hand, when such a silver halide photographic material capable of magnetic recording is used, information is taken in and out of the magnetic recording layer by using a so-called magnetic head, but the number of tracks of the magnetic head is increased to increase the amount of information. On the contrary, the width of one track is often very narrow. In such a case, if the dimensional change of the film due to changes in temperature and humidity is large, the position where the magnetic information is written and the position where the magnetic information is read are displaced,
Output error may occur. Therefore, a support for such a light-sensitive material is required to have extremely good dimensional stability. Further, when the longest possible light-sensitive material is incorporated into a given cartridge, or conversely, when the light-sensitive material having a given length is incorporated into a compact cartridge, the support is preferably as thin as possible. However, when the support is made thin, mechanical strength is weakened, which causes breakage and bending, which causes inconvenience. Therefore, such a sensitive material requires a support having a mechanical strength as high as possible.
As described above, cellulose triacetate, which has been conventionally used as a photographic light-sensitive material, is an unsuitable material as a support having excellent dimensional stability and mechanical strength. Considering that, the most suitable material is polyester. However, when a magnetic recording layer is further provided using a polyester support, if a polymer other than polyester such as vinyl chloride is used as the binder of the layer containing the magnetic material, the adhesion to the support will be poor and rubbing with a magnetic head will occur. There was a problem that the magnetic recording layer was peeled off during the operation. Further, when the magnetic recording layer is installed by coating with an organic solvent, there is a problem of environmental deterioration due to the evaporated organic solvent. Further, a new step of separately coating the magnetic recording layer is required, and there is an unfavorable problem from the viewpoint of production rationality. Therefore, development of a method for solving these problems has been desired.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having a magnetic recording layer with less magnetic output error. Another object is to provide a silver halide photographic light-sensitive material having a magnetic recording layer, which has good adhesion between the support and the magnetic recording layer. Still another object is to provide a silver halide photographic light-sensitive material having a magnetic recording layer, which can be manufactured in an integrated process without deteriorating the environment in production.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material containing a ferromagnetic fine powder in a transparent support, wherein the support contains a polyester fine film layer (A) containing the ferromagnetic fine powder. ) And a polyester film layer (B) containing no ferromagnetic powder to obtain a silver halide photographic light-sensitive material. Even more surprisingly, a polyester having polyethylene terephthalate as a main component, which is composed of a polyester having a hydrophilic group in at least one of the polyester films (A) and (B), or is mixed with a substance having water absorbability is used. It was further found that a silver halide photographic light-sensitive material with less magnetic output error was obtained.

Next, the polyester support used in the present invention will be described in detail. In the present invention, the polyester is a polyester having a dibasic acid and glycol as main constituent components. Polyethylene terephthalate (PET) is well known as a conventional polyester material, and in the present invention, the polyester having a hydrophilic group refers to a polyester having a higher water content than PET. The hydrophilic group in the polyester of the present invention may be introduced into either a dibasic acid or a glycol which is a constituent component. Examples of the hydrophilic group that can be introduced include sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or salts thereof, polyalkyleneoxy group, alkoxy group, alkoxycarbonyl group, sulfamoyl group, carbamoyl group, acylamino group, sulfonamide group, disulfone. Examples thereof include various mono- or divalent substituents such as amide group, ureido group, urethane group, alkylsulfonyl group, and alkoxy group. Among them, sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid Alternatively, a salt thereof, a polyalkyleneoxy group and a disulfonamide group are particularly preferable.

Among the constituents having such a hydrophilic group, preferred dibasic acids are 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid and 4-sodium sulfoterephthalic acid.
Sodium sulfophthalic acid, 4-sodium sulfo-
2,6-naphthalenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid monosodium salt,

[0007]

[Chemical 1]

[0008]

[Chemical 2]

And the like. In these dibasic acids, the compound having a sodium salt may be a compound substituted with a hydrogen atom or another metal atom such as lithium or potassium. The carboxyl group in these dibasic acids may be esterified (alkyl or aryl ester) or may be used in the form of acid chloride, depending on the production requirements. Preferred glycols having a hydrophilic group include HO- (C
_{H 2) 2 - (OCH 2} CH 2) n -O (CH 2) 2 - O
H (n represents an integer of 1 to about 20), HO- (CH
_{(CH 3) CH 2 O)} n -H (n is an integer of 2 to about 20),

[0010]

[Chemical 3]

And the like. In addition to these, hydroxy polyester, hydroxy polyacetal, and hydroxy ester amides can be used as the diol component. A polyester having a hydroxy group is a reaction product of a polyhydric (mainly divalent) alcohol and a dibasic carboxylic acid. Hydroxy acetals can be obtained from glycols (eg diethylene glycol) and formaldehyde. The hydroxy ester amide is, for example, a condensate obtained from a dibasic carboxylic acid and amino alcohol alone or a mixture of diamine and polyamines. As the constituent component of the polyester of the present invention, various compounds other than those listed above can be used. Dibasic acids that can be used include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride,
Succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, diphenylene-P, P'-dicarboxylic acid, tetrachloro Phthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid,

[0012]

[Chemical 4]

[0013]

[Chemical 5]

And the like. Usable diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane. Diol, 1,8-octanediol, 1,10-decanediol, 1,12-
Dodecanediol, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol, catechol, resormine, hydroquinone, 1,4
-Benzenedimethanol,

[0015]

[Chemical 6]

[0016]

[Chemical 7]

And the like. If necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. Further, the polyester of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule. Examples of such compounds include:

[0018]

[Chemical 8]

The polyester of the present invention is particularly preferably a copolyester whose main components are ethylene glycol and terephthalic acid. The hydrophilicity and the amount of the constituents to be introduced into such a copolyester may be variously changed depending on the hydrophilicity of the constituents themselves and the physical properties of the resulting polyester (refractive index, mechanical strength, etc.). It is preferably from 1 to 50% by weight, particularly preferably from 2 to 40% by weight, based on the total weight of the polyester. Further, ethylene glycol, terephthalic acid, and copolymerizable constituents other than the hydrophilic constituents also have physical properties such as hydrophilicity, refractive index, transparency, glass transition temperature, melting point, and folding endurance of the resulting polyester. Considering the mechanical and mechanical properties,
Although it can be introduced arbitrarily, the amount thereof is preferably 0 to 50% by weight, particularly preferably 0 to 40% by weight, based on the total weight of the polyester.

The polyester of the present invention can be synthesized by a conventionally known polyester production method. For example, the acid component can be directly esterified with the glycol component, or when the acid component is used as a dialkyl ester, a transesterification reaction with the glycol component can be used. Alternatively, the acid component is set as an acid halide,
It may be reacted with glycol. At this time, if necessary, a transesterification reaction catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. Regarding the polyester constituent components and the synthesis method described above, for example, Polymer Experimental Science Vol.
Years) 103-136, "Synthetic Polymer V" (Asakura Shoten, 1971), pages 187-286. The preferred average molecular weight range for the polyesters used in this invention is from about 3,000 to about 1.
It is 0,000. Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Numbers in the polyester compound example () indicate the molar ratio of each component.

P-1 TPA / AA / SSIA / EG (88 / 5.3 / 6.7 / 100) P-2 TPA / AA / SSIA / EG (90 / 7.2 / 2.8 / 100) P -3 TPA / AA / SSIA / EG (88 / 7.2 / 4.8 / 100) P-4 TPA / SSIA / EG / DEG (95/5/85/15) P-5 TPA / SSIA / EG / TEG (93/7/80/20) P-6 TPA / AA / SPIA / EG (90/4/6/100) P-7 TPA / PEG (4000) / EG (100 / 0.5 / 99.5) ) P-8 TPA / IPA / SSIA / PEG (4000) / EG (95/4/1 / 0.3 / 99.7) P-9 TPA / SSIA / SA / TEEG / EG (95/3/2 /) 5/95) P-10 TPA / SCPP / AA / EG (90/5/5/100) P-11 TPA / AA / SSIA / EG / DEG (88/5/7/90/10) P-12 TPA / PISB / AA / EG (94/3/3/100) ) P-13 TPA / PISB / EG / DEG (97/3/95/5) P-14 TPA / EG / DMPS (100/95/5) P-15 TPA / SSIA / SA / EG / BHPP (90 / 2/8/95/5) Abbreviation explanation

[0022]

[Chemical 9]

[0023]

[Chemical 10]

The above-mentioned copolymerization ratio is the molar ratio of the dibasic acid components charged. Of the glycol components, the components other than EG represent the charged mole percentage with respect to the total acid components. EG is used in excess with respect to the acid component in accordance with the synthesis using the usual transesterification method. I wrote it.

Next, the substance having water absorbability mixed with polyethylene terephthalate will be described. Examples of the substance having water absorption include, in addition to the above-mentioned polyester having a hydrophilic group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, a carboxylic acid group, and salts thereof, a polyalkyleneoxy group, an alkoxy group, an alkoxy group. A polymer having at least one functional group of a carbonyl group, a sulfamoyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a disulfonamide group, a ureido group, a urethane group, an alkylsulfonyl group, and an alkoxysulfonyl group,
Alternatively, alkali metal, alkaline earth metal, Si, A
l, Zr, Mo, Fe, Sb, Pb oxides, sulfides,
Sulfates, sulfites, carbonates, hydroxides, halides,
There are inorganic substances containing at least one compound of nitrates, and these polymers and inorganic substances may be used in combination. Examples of water-absorbing polymers include polyacrylic acid and polymethacrylic acid and their derivatives, polyacrylamide and its derivatives, polyethylene glycol and its derivatives, polystyrene sulfonate and its derivatives, polyethylene oxide and its derivatives, and the like. Can be mentioned. Many kinds of these polymers are commercially available and can be easily obtained and used.

A film can be formed into a film by blending these water-absorbing polymers and PET and by an extrusion method or the like. At this time, the blending ratio of PET and these polymers is preferably 20 to 95% by weight of PET,
It is more preferably 30 to 80% by weight. this is,
This is because if the PET content is too large, the water absorption into the support is insufficient, and if it is too small, the heat resistance of the PET decreases. These polymers may be compatible with PET, or may be phase-separated as long as they have transparency. Further, various compatibilizers may be added for the purpose of improving compatibility.

PE having such water-absorbing polymer
The ratio of T is 1 to 50% by weight, preferably 3 to 30% by weight.

Typical examples of the above-mentioned water-absorbing inorganic compound include silica, alumina, calcium carbonate, magnesium carbonate, kaolin, clay, talc, titanium oxide and the like. These are commercially available and can be easily obtained. These compounds may be added to PET as they are, or may be subjected to surface treatment (for example, addition of long-chain fatty acid or silane coupling treatment) in order to improve affinity with PET.

If the amount added is too small, there is no effect, and if it is too large, it causes haze.
0.1 to 30% by weight, and more preferably 0.2 to 20% by weight. This addition may be carried out by adding these inorganic compounds during or after the polymerization of the polymer, or by adding these inorganic compounds in the form of a precursor to the polymer polymerization system to obtain the desired inorganic compound during the polymerization reaction. good.

When the polyester is used in the layer containing the ferromagnetic fine powder and the layer not containing the ferromagnetic fine powder, the normal polyester, the polyester having the hydrophilic group as described above, and the polyethylene terephthalate in which the substance having the water absorbing property is mixed are used. Either of the polyesters as the main component may be provided in either layer, but preferably, the main component is the polyester having a hydrophilic group as described above or the polyethylene terephthalate mixed with the substance having water absorbability. It is better to use polyester for at least one side. The layer containing no ferromagnetic fine powder may be a laminate of two or more layers.

The ferromagnetic fine powder used in the present invention includes ferromagnetic iron oxide fine powder, Co-containing ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder, ferromagnetic alloy powder, barium ferrite. Etc. can be used. As an example of the ferromagnetic alloy powder, the metal content is 75 wt% or more, and 80 wt% or more of the metal content is at least one type of ferromagnetic metal or alloy (Fe, Co, Ni, Fe-C).
o, Fe, Ni, Co-Ni, Co-Fe-Ni, etc., and other components (Al, S
i, S, Se, Ti, V, Cr, Mn, Cu, Zn,
Y, Mo, Rh, Pd, Ag, Sn, Sb, B, Ba,
Ta, W, Re, Au, Hg, Pb, P, La, Ce,
Pr, Nd, Te, Bi, etc.) can be included. Further, the ferromagnetic metal component may contain a small amount of water, hydroxide, or oxide. The method for producing these ferromagnetic powders is known, and the ferromagnetic powders used in the present invention can also be produced according to known methods. The ferromagnetic fine powder has a needle shape,
It may be rice grain, spherical, cubic, plate-shaped, etc.
The needle-like shape and the plate-like shape are preferable in terms of electromagnetic conversion characteristics. In the acicular form, the crystallite size is preferably an average particle size of 0.04 to 3 μ, and the particle size ratio (major axis / minor axis) of 2 to 15 is preferable. In the plate-like particles such as barium ferrite, the average particle size is 0. .04-3
μ, and the thickness is preferably 1/2 to 1/20 of the particle size. The pH and surface treatment of the ferromagnetic powder can be used without particular limitation (the surface may be treated with a substance containing an element such as titanium, silicon or aluminum, or may be carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, It may be treated with an organic compound such as a phosphate ester, an adsorptive compound having a nitrogen-containing heterocycle such as benzotriazole). The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron. The addition amount of ferromagnetic fine powder is 1
Per m ² , 0.01 to 1 g, preferably 0.03 to
It is 0.5 g. The thickness of the layer containing ferromagnetic fine powder is 10
It is preferably μ or less, more preferably 5 μ or less. These ferromagnetic fine powders may be used alone or as a mixture.

When the ferromagnetic fine powder is added to the polyester layer, various additives such as a dispersant, a lubricant and an antistatic agent can be added. As a dispersant,
Fatty acids having 12 to 18 carbon atoms such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and stearolic acid, and metallic soaps composed of alkali metal or alkaline earth metal of these fatty acids Further, higher alcohols and higher esters are also used.

Examples of the lubricant include silicone oil such as polysiloxane, carbon black, graphite,
Examples thereof include inorganic fine powder such as molybdenum disulfide, plastic fine powder such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, and fluorocarbons. These may be used alone or in combination. The addition amount of these is preferably in the range of 0.2 to 20 parts by weight with respect to 100 parts by weight of the binder. Examples of the abrasive include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specifically, aluminum oxide (α-alumina, γ-alumina, fused alumina, corundum, etc.), oxidation Chrome (Cr
₂ O ₃ ), iron oxide (α-Fe ₂ O ₃ ), silicon dioxide, titanium dioxide, and other oxides, silicon carbide, titanium carbide, and other carbides, and diamond and other fine powders. The average particle size of these is preferably 0.05 to 1.0 μm,
It can be added in an amount of 0.5 to 20 parts by weight with respect to 100 parts of the ferromagnetic powder. As the antistatic agent, carbon black (particularly preferably having an average particle size of 10 to 300 nm), graphite, conductive powder such as carbon black graphite polymer, nonionic surfactant, anionic surfactant, cationic interface Activators and the like are used. The polyester containing the ferromagnetic fine powder and other additives may be coated on the polyester film after dispersing the ferromagnetic fine powder as a solution in a suitable solvent, but the polyester containing the ferromagnetic fine powder is preferable. And the polyester containing no ferromagnetic fine powder are melted, and a co-extrusion die is used to form a laminated sheet. At this time, the polyester is melted and heated at a high temperature of at least 10 ° C., which is the melting point of each polyester, then uniformly dispersed by a melt extruder, a biaxial or uniaxial kneader, and then extruded in a sheet form from a ring die or a flat die. The thickness of the polyester film layer (A) containing ferromagnetic fine powder is 0.5 to 5
It is 0 μ, preferably 1 to 10 μ. On the other hand, the thickness of the polyester film layer (B) containing no ferromagnetic fine powder is 1
It is 0 to 300 μ, preferably 50 to 200 μ. Before the sheet extruded from the die is solidified, the sheet is passed through the sheet so that the direction of magnetic lines of force traverses the sheet. Magnetic field is 500 ~
An electromagnet, an air-core solenoid coil, etc. are provided close to the sheet in the range of 3500 gauss. In addition, the direction of magnetic force lines can be set according to the purpose. The polymer sheet that has been subjected to the magnetic field is introduced into a cooling drum, a cold water bath or the like and is cooled and solidified. After being solidified by cooling, it may be uniaxially stretched in the machine direction (longitudinal direction) or may be biaxially stretched in the machine direction and the width direction simultaneously or sequentially as required. In the case of stretching in the machine direction, the temperature is in the range of from the glass transition point of the polymer to the melting point, and is about 2-10 times. The silver halide emulsion layer is preferably provided on the polyester film layer (B) containing no ferromagnetic fine powder, and the polyester film may be subjected to surface activation treatment, or after the surface treatment,
Alternatively, an undercoat layer is provided without surface treatment and a silver halide emulsion layer is provided. As surface treatment, chemical treatment,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment and the like are used.

The polyester support of the present invention preferably has a subbing layer in order to increase the adhesive force with a photographic layer such as a photosensitive layer coated thereon. As the subbing layer, a subbing layer using a polymer latex composed of a styrene-butadiene-based copolymer or a vinylidene chloride-based copolymer,
There is a subbing layer that uses a hydrophilic wing such as gelatin. The subbing layer preferably used in the present invention is a subbing layer using a hydrophilic binder. Examples of the hydrophilic binder used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, and the like, and cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose. And so on. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferred.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Among these, resorcin and p-chlorophenol are preferable. Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin. And so on. The subbing layer of the present invention includes SiO ₂ and TiO ₂ .
₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. The undercoat layer according to the present invention may be applied by a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain funnel method, a wire bar coating method, a gravure coating method, an extrusion coating method, or the like. It is possible.

The silver halide emulsion layer may be black-and-white or color. Here, the color silver halide photographic light-sensitive material will be described. The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is a unit photosensitive 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, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-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 the same color-sensitive layers. A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer is provided with JP-A-61-43.
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, etc. as described in the specification, and may contain a color mixing inhibitor as commonly used. .. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,4.
70 or British Patent No. 923,045, JP-A Nos. 57-112751, 62-200350 and 6
No. 2-206541, No. 62-20654.3, No. 5
6-25738, 62-63936, 59-2.
No. 02464, Japanese Patent Publication No. 55-34932, 49-1
5495. Silver halide grains have regular crystal shapes such as cubes, octahedra and tetradecahedrons, irregular crystal shapes such as spheres and plates, and crystal defects such as twin planes. It may have one or a combination thereof.

The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid.
716 (November 1979), p.648, Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Gl.
afkides, Chemie et Phisiqu
e Photographique, PaulMont
El, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photo.
graphic Evolution Chemistr
y (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al., Maki).
ng and Coating Photograph
ic Emulsion, Focal Press, 1
964) and the like. U.S. Pat. Nos. 3,574,628 and 3,65
The monodisperse emulsions described in, for example, 5,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutof).
f, Photographic science an
d Engineering), Volume 14, 248-2
57 (1970); U.S. Pat. No. 4,434,226.
Issue No. 4,414,310 Issue 4,433,048
No. 4,439,520 and British Patent No. 2,11.
It can be easily prepared by the method described in No. 2,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. The additives used in such a process are Research Disclosure N.
o. 17643 and No. 17643. 18716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also the above-mentioned two research products.
It is described in the disclosure, and the relevant parts are shown in the table below.

[0039] Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound which can be immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 is used as a light-sensitive material. It is preferable to add.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G
Are described in the patents listed in. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961
No. 5, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
5,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649, and European Patent 249,473A.
And the like are preferred. As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897, European Patent 73,636, and US Pat. 061,432 and 3,725,06
No. 7, Research Disclosure No. 24220
(June 1984), JP-A-60-33552, Research Disclosure No. 24230 (1984
June), JP-A-60-43659, 61-722.
No. 38, No. 60-35730, No. 55-118034.
No. 60-185951, U.S. Pat. No. 4,500,
No. 630, No. 4,540, 654, No. 4,55
Those described in 6,630, WO (PCT) 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,753,871, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable. A colored coupler for correcting unnecessary absorption of a coloring dye is Research Disclosure No.
17643, Section VII-G, U.S. Pat. No. 4,16.3.
670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,
Those described in 004,929, 4,138,258 and British Patent 1,146,368 are preferable. Examples of couplers in which the color forming dye has excessive diffusibility include U.S. Pat. No. 4,366,237 and British Patent 2,125,
570, European Patent 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.
Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,080,211.
No. 4, No. 4,367,282, No. 4,409,32
No. 0, 4,756,910, British Patent 2,10
2, 137, etc.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler releasing a development inhibitor is the above-mentioned R
D17643, Patents described in VII to F, JP-A-57-151944, JP-A-57-154234, and JP-A-57-154234.
Those described in 0-184248, 63-37346 and U.S. Pat. No. 4,248,962 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, and JP-A-59-157638.
Nos. 59-170840 and No. 59-170840 are preferable.
Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130.427, US Pat. Nos. 4,283,472 and 4,338,393. No. 4,310,618 and the like, multiequivalent couplers, JP-A-60-185950.
No. 1, JP-A-62-24252, DIR redox compound releasing captor, DIR coupler releasing coupler, DIR coupler releasing redox compound or DI.
R redox-releasing redox compounds, EP 17
No. 3,302A, a coupler that releases a dye that recovers color after separation, R.I. D. No. 11449, 24241,
Bleach accelerator releasing couplers described in JP-A-61-2201247, ligand-releasing couplers described in U.S. Pat. No. 4,553,477, and leuco dyes described in JP-A-63-75747. Examples thereof include couplers. The tumbler 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. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, and aniline derivatives. Rest, hydrocarbons and the like can be mentioned. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less, and the film swelling speed T1.
/ 2 is preferably 30 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T1 / 2 can be determined according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129, T1 / 2 can be measured by using a color developing solution at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swelling thickness reached is defined as the saturated film thickness, which is defined as the time until the film thickness reaches T1 / 2. The film swelling speed T1 / 2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating.
The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above, using the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, and ibid. Development can be carried out by a usual method described in the left column to the right column of 615 of 18716. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat. Nos. 3,342,597, indoaniline compounds, 3,342,599, Research Disclosure 14,850 and 1
Schiff base type compounds described in No. 5,159, and No. 13,9
24.

Next, the novel photographic system described in claim 10 will be described. The first feature of this system is
It is easy to load the film into the camera. In conventional photographic film cartridges, the photographic film is not tightly wound on the spool inside the cartridge, but is stored in a loosely wound state, so even if the spool is rotated in the direction opposite to the film winding direction, the photographic film will not be wound outside the cartridge. Could not be sent to. Therefore, it is necessary to pull out the photographic film front end to an appropriate length in advance from the outside of the cartridge, and the photographer must load the photographic film front end into the film feeding mechanism in the camera.

However, this operation is time-consuming and requires a certain amount of skill, so that a loading error often occurs, and when a loading error occurs, an unphotographed photographic film is exposed. was there. Therefore, a camera system that does not require such an operation has been desired.

Such a camera system can be realized by allowing the photographic film to be sent out from the inside of the cartridge. If the photographic film can be sent out from the inside of the cartridge, the film can be engaged with the film feeding mechanism in the camera by sending out the leading edge of the film, so the operation of loading the film end into the film feeding mechanism in the camera It becomes unnecessary.

For such a purpose, a patrone which has been conventionally used cannot be used, and a new one must be used. The patrone will be described below. This patrone is mainly composed of synthetic plastic. To mold this plastics, a plasticizer is mixed with the plastics if necessary. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone, di-n-octyl succinate, bromonaphthalene, and butyl palmitate. It is something.

Specific examples of the plastics material used in the present invention are shown below, but the invention is not limited thereto. Specific examples include 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. The antistatic agent is not particularly limited, but carbon black, metal oxide particles, nonion, anion,
Cation and betaine-based surfactants or polymers can be preferably used. These antistatic batrones are disclosed in JP-A 1-312537 and 1-31.
2538.

In particular, the resistance at 25 ° C. and 25% RH is 10
^It is preferably ¹² Ω or less. Usually, Patrone is made of plastic in which carbon black, pigments, etc. are kneaded in order to impart a light-shielding property. The size of the cartridge may be the same as it is now, or the current cartridge diameter of 25 m / m may be 22 m / m or less, preferably 20 m / m or less,
If it is 14 m / m or more, it is effective for downsizing the camera.

The volume of the cartridge case is 30 cm ^3.
It is preferably 25 cm ³ or less, more preferably 20 c or less.
It is preferably m ³ or less. The weight of the plastic used for the cartridge and the cartridge case is 1 g or more and 25 g or less, preferably 5 g or more and 15 g or less.

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

In the case of a patrone containing the preferred 135 color light-sensitive material in the present invention, the total weight of the plastic used in the patrone and the patrone case is usually 1
It is g or more and 25 g or less, preferably 5 g or more and 15 g or less. The Patrone of the present invention is not particularly limited with respect to its shaped bear.

It is preferable to use it in a new camera adapted to a cartridge in which the light-sensitive material of the present invention is incorporated. These specific cartridges are shown in FIG.
~ Fig. 4 further describes a cartridge used in the present invention to rotate a spool to feed a film. An example of the patrone is the patrone described in Japanese Patent Application No. 1-21862.

5 and 6 show a patrone used in the present invention. The photographic film cartridge 120 includes a spool 101 and one end of which is locked to the spool 101.
1. A photographic film 102 and a cartridge main body 103 wound in a roll shape. The spool 101 is attached to the inside of the cartridge main body 103 so as to be rotatable around its axis.
The cartridge main body 103 can be rotated from the outside. The cartridge main body 103 is provided with a photographic film drawer 104 for drawing out the photographic film 102, and the inside of the photographic film drawer 104 is shaded inside the cartridge main body 103. Light-shielding member 10 for keeping the state
4a is attached.

In the photographic film cartridge 120, which extends in the circumferential direction along the inner surface of the cartridge body 103 and has a width of about 15 to 20% of the film width--a pair of ribs 108 are provided at both ends in the width direction of the film 102. It is provided in the section. The rib 108 is opened in the direction of the film pull-out port 104 so that the photographic film 102 can be pulled out from the film pull-out port 104. Also,
The leading edge 106 of the film 102 is arranged so as to match the leading edge 107 of the photographic film drawing port 104.

The rib 108 contacts the outermost peripheral surface of the film 102 and presses the rolled film 102 from the outermost peripheral surface to keep the film 102 tightly wound on the spool 101.

The outer diameter of the spool 101 is determined as follows. As described above, it is difficult to tightly wind the film 102 on the spool 101 while keeping the innermost peripheral surface 102a of the film in contact with the outer periphery of the spool 101. Therefore, it is unavoidable that a gap is formed between the innermost film peripheral surface 102a and the spool 101. As described above, if the space h between the innermost film peripheral surface 102a and the spool 101 is too large, the reversal phenomenon of the film 102 as shown in FIG. 7 occurs. Therefore, the spool 10
The outer diameter of 1 is the innermost peripheral surface 102a of the film and the spool 101.
When a gap is created between the two, the distance h between them is set to 2 mm or less. That is, the outside diameter a of the spool
Is b / 2 = a / 2 + h + c.d + t, where b is the inside diameter of the cartridge, t is the thickness of the rib, c is the thickness of the film, and d is the number of rolls that change depending on the film length. , A / 2 = b / 2−th−h−c · d. Since the interval h is h = b / 2−a / 2 = c · d−t, the outer diameter a of the spool when h ≦ 2 mm is satisfied.
Is b / 2−t−c · d−2 ≦ a / 2.

By setting the interval h to 2 mm or less, and setting the spool rotation torque to 0.8 kgf · cm or less, the reversal phenomenon of the photographic film 2 can be prevented. The ribs 108 do not need to be provided in the entire circumferential direction along the inner surface of the cartridge main body 103, and may be provided only in a part of the inner surface of the cartridge main body 103 in the circumferential direction. Further, as in the present embodiment, it may be provided only at both ends in the width direction of the film 102, or may be provided over the entire width direction of the film 102.

The rib 108 is made of a material, such as plastic, which does not easily damage the film 102 (but is not perfect). In this case, a member having some elasticity such as urethane may be selected. If the thickness of the ribs 108 is determined so that the ribs 108 made of urethane contract when the film 102 is tightly wound on the spool 101 and loaded in the cartridge body 103, the elastic force of the contracted ribs 108 causes the film to be compressed. 10
Since the outer circumference of the second roll is pressed, it is possible to keep the film 102 tightly wound even if the film 102 is pulled out by a considerable length and the outer diameter of the roll of the film 102 becomes small.

Any method can be used to shield the film outlet. A felt-shaped light-shielding member called "telemp" may be provided as in the conventional case, or the film outlet may be formed to be openable and closable and kept closed except when necessary. Also, the tip 1 of the film 102
06 is always the tip 107 of the film outlet 104
It is not necessary to arrange it according to
It may be stored inside, but the film outlet 1
It is desirable to be stored in 04.

Furthermore, a patrone described in Japanese Patent Application No. 1-172594 can be used. These are types in which the film is fed by deforming the spool flange and rotating the spool while also pressing the end face of the outermost peripheral portion of the film roll. In FIG. 8 showing a state in which the photographic film cartridge is disassembled, a photographic film cartridge 201 includes a spool 206 on which a photographic film 205 is wound in a roll shape, and a cartridge body 2 for storing the spool 206.
07, and side plates 208 and 209 that rotatably support the spool 206 and close the cartridge body 207 in a light-tight manner from the side.

The spool 206 has a flange 206a thinly formed so as to have flexibility, and an inflexible flange 206b thickly formed, and is integrally formed of plastic. Photographic film 205
The end portion thereof is fixed to the spool 206 between the flanges 206a and 206b, and the end surfaces of the respective ends are fixed to the flange 206
It is wound around the spool 206 in a roll shape along the insides of the a and 206b, and is completely wound up in the cartridge body 207 up to the tip. The Patrone body 2
At 07, a film entrance / exit 212 to which a light-shielding telem 211 is joined is provided.

At the center of the side plate 208, the spool 2
A bearing opening 208a that rotatably supports the end portion 206c (see FIG. 9) of 06 is provided, and a ridge portion 208b that presses a part of the flange 206a is provided on the inner wall surface. The spool 206 is provided at the center of the side plate 209.
Bearing opening 209 for rotatably supporting the end portion 206d of the
a is provided, and in the vicinity thereof, a projection 209b for reducing friction between the inner wall surface of the side plate 209 and the flange 206b.
(See FIG. 9) are provided.

In FIG. 7 showing the longitudinal section of the photographic film cartridge 201, the inner dimensions of the ridges 208b and the protrusions 209b are set to be smaller than the outer dimensions of the flanges 206a and 206b. The flange 206a is pressed and deformed. by this,
The end surface of the photographic film 205 on the outer side is more strongly sandwiched between the films 206a and 206b than on the inner side. Therefore, if the spool 206 is rotated in the direction of arrow A shown in FIG.
The front end portion 205a of the photographic film 205 is sent to the outside of the cartridge main body 207 through the film entrance / exit 212 by frictional engagement with the five end faces.

Further, in the above structure, the ridge portion 20
8b and the protrusion 209b, the inner dimension of the flange 206a,
It can be larger than the outer dimension of 206b. In that case, the spool 206 should be attached to the flange 2 of the camera component.
By pushing from 06b toward the flange 206a,
The inner dimensions of the flanges 206a and 206b are smaller than that of the photographic film 205, so that the end surface of the photographic film 205 can be pressed, and the photographic film 205 can be sent to the outside of the cartridge body 207 by the rotation of the spool 206.

Furthermore, US Pat. Nos. 4,834,306 and 484 are also included.
Patrone described in Nos. 6418 and 4832,275 is preferably used. (FIGS. 10, 11 and 12) As an example of them, as shown in FIG. 10, the photographic film 76 densely wound in a roll shape on the spool 75 is densely wound on the spool 75 by a pair of rings 77a and 77b at both ends thereof. It is kept rolled. Inside the cartridge body 78, grooves 79a, 79 in which the rings 77a, 77b are fitted.
b is formed so as to be inclined with respect to the axial direction of the cartridge body 78. Therefore, as shown in FIGS.
As shown in FIG. 2, the rings 77a and 77b contact the outer circumference of the roll of the photographic film 76 at an angle inclined with respect to the axis of the spool 75 inside the cartridge main body 78 to prevent the photographic film 76 from being loosened. .. Ring 77
a and 77b slide in the grooves 79a and 79b,
It is rotatable along 9a and 79b.

The photographic film 76 includes rings 77a and 77b.
Since the spool is kept tightly wound around the spool 75, the photographic film 76 is sent out from the photographic film outlet (not shown) when the spool 75 is rotated in the direction opposite to the film winding direction. ..

As described above, it is necessary to reduce the thickness of the film in order to insert the film of the same length even if the diameter of the cartridge is reduced. Furthermore, in the case of the cartridge having the above-mentioned feeding mechanism, the mechanical strength of the film itself is required. Therefore, as the film material, polyester is advantageous as a thin material having high strength. Further, as described above, when the cartridge size becomes smaller, so-called curl tends to be formed, but when the film having a hydrophilic or water-absorbing component as in the present invention has a smaller curl, it is an advantageous direction. ..

[0071]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 [Preparation of polyethylene terephthalate film] 100 parts by weight of dimethyl terephthalate, ethylene glycol 7
0 part by weight, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate and 0.03 part of antimony trioxide.
Part by weight was added, and transesterification was carried out by a conventional method. 0.05 parts by weight of phosphoric acid trimethyl ester was added to the obtained product, the temperature was gradually raised and the pressure was reduced, and finally 280 ° C.
Polymerization was performed at 1 mmHg or less to obtain polyethylene terephthalate [A]. On the other hand, polymerization was carried out in the same manner except that dimethyl 5-sodium sulfoisophthalate and dimethyl adipate were replaced with equivalent amounts of dimethyl terephthalate,
Polyethylene terephthalate [B] was obtained.

As ferromagnetic fine powder, acicular Co-doped γ-ferric oxide (Hc = 700) having an average particle size of 0.3 μ and a particle size ratio of 8
1 part by weight of Oe), 0.02 part by weight of calcium carbonate, 0.1 part by weight of calcium stearate, and 60 parts by weight of polyethylene terephthalate [A] described above are uniformly kneaded by a twin-screw type kneader, and at 290 ° C. Melt and extrude. Separately, polyethylene terephthalate [B] 290
Melt extrude at ℃. These extrusions were extruded from a co-extrusion die by adjusting the lip intervals to obtain laminated sheets. The laminated sheet was stretched 3.3 times in the machine direction at 90 ° C, and then stretched 3.0% in the width direction at 105 ° C.
Stretched twice and heat set at 210 ° C for about 5 seconds,
A laminated sheet sample (Sample 10 containing 5 μm of the layer containing the ferromagnetic fine powder and 120 μm of the layer containing no ferromagnetic fine powder).
1) was obtained. On the other hand, a sample 102 was obtained in the same manner as the sample 101 except that polyethylene terephthalate [B] was used as the binder for the layer containing the ferromagnetic fine powder. Sample 1 except that the binder of the layer containing no ferromagnetic fine powder was polyethylene terephthalate [A]
Sample 103 was obtained in the same manner as 01. Further, a sample 104 was obtained in the same manner as the sample 103 except that polyethylene terephthalate [B] was used as the binder of the layer containing the ferromagnetic fine powder. On the other hand, a polyethylene terephthalate sheet having no layer containing ferromagnetic fine powder was prepared using Sample 101, and a solution prepared by dispersing the ferromagnetic fine powder with a polymer having the following formulation using a sand mill was applied to give a coating thickness of 5 μm.
Then, a ferromagnetic fine powder was coated so as to be contained in the same amount as the sample 101 to prepare a comparative sample 105.

Next, the same ferromagnetic fine powder was dispersed in cellulose triacetate using a sand mill to prepare a dope solution (A) having the following composition, and another dope solution (B) was prepared and dried. Membrane (A), (B) each 5
The film was formed by co-casting (A) as an upper layer on the casting band using a composite slit die so that the film thickness became μ, 120 μ. Also in this case, the amount of ferromagnetic fine powder to be installed was 10
I made it the same as 1. Sample 10 for comparison
6 On the other hand, using only the above-mentioned dope liquid (B), a thickness of 120 μm
The ferromagnetic fine powder / polymer solution used in Sample 105 was coated on the base film formed so that the coating thickness was 5 μm and the amount of ferromagnetic fine powder applied was equal to that of Sample 101. And a comparative sample 107 was prepared.

For each of Samples 101 to 107, 0.0 was added to the polyester layer side containing no ferromagnetic fine powder.
After a corona discharge treatment of ² KVA min / m ² , an undercoat layer having the following composition was provided. Further, on the undercoat layer, JP-A-2-44345,
An emulsion layer for the color negative light-sensitive material described in Example Sample 101 was coated. When these light-sensitive materials were developed by the method described in the examples of the same patent and subjected to sensitometry, they showed the same good performance as a normal light-sensitive material containing no ferromagnetic fine powder.

The following evaluation tests were carried out on Samples 101 to 107 coated with these silver halide emulsion layers. The results are shown in Table 1. It can be seen from Table 1 that the sample of the present invention shows significantly superior performance to the comparative sample in various physical properties such as magnetic output, adhesion and strength.

[0076]

[Table 1]

(Magnetic output performance) Each sample has a width of 35 mm
Slit into, head gap 5μ, number of turns 100
0, using a 4-channel audio head with a track width of 0.4 mm and capable of input / output, at a feed rate of 30 mm / sec.
The digital signal of KHZ was recorded. After that, each sample was stored at 60 ° C. and 70% for 3 days, and then an output test was conducted 1000 times with the same head to determine the error occurrence rate. (Adhesion Performance) Each sample was left in an atmosphere of 25 ° C. and 70% RH for 2 weeks, and then tested by the following method.
On the side of the layer containing ferromagnetic fine powder, the vertical and horizontal 5 mm intervals
Make cuts for each book to make 36 squares, and adhesive tape (Nitto tape manufactured by Nitto Denki Kogyo Co., Ltd.) on this
Glue and quickly peel off in 180 ° direction. In this method, the area of the unpeeled portion is 90% or more of A grade, 60
90% to B class, less than 60% to C class. (Strength performance) Using a light load spread tear strength test base (manufactured by Toyo Seiki Co., Ltd.), 1 with sample size 51 × 64 mm
A cut value of 3 mm was put in, and the indicated value when the remaining 51 mm was torn was read.

Example 2 Example 1 was repeated except that instead of dimethyl 5-sodium sulfoisophthalate in Example 1, disodium 3,5-di (methyloxycarbonyl) phenylphosphonate was used.
When a sample was prepared and evaluated in the same manner as in Example 1, Example 1
Similar results were obtained.

Example 3 Samples of the present invention and comparative samples were prepared in the same manner as in Example 1 except that barium ferrite (Hc = 650 Oe) having an average particle size of 0.6 μ was used as the ferromagnetic fine powder. When evaluated, the same results as in Example 1 were obtained.

[0080]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a laminated silver halide photographic light-sensitive material in which the magnetic output is remarkably improved, the magnetic recording layer has good adhesion and the mechanical strength is high.

[Brief description of 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 the leading end portion of the photographic film in FIG.

FIG. 3 is a sectional view of the cartridge of FIG.

FIG. 4 is a partially cutaway view of the cartridge of FIG.

FIG. 5 is a side view of a photographic film cartridge according to the present invention.

FIG. 6 is a front view of the above.

FIG. 7 is a side view of a photographic film cartridge according to the present invention.

FIG. 8 is an overall view of a photographic film cartridge according to the present invention.

FIG. 9 is an internal view of a photographic film cartridge according to the present invention.

FIG. 10 is an outer case diagram of a photographic film cartridge according to the present invention.

FIG. 11 is a state diagram of the inner spool and the photo film of the above.

[FIG. 12] Same as above

[Explanation of symbols]

 1 Photo Film Patrone 2 Spool 3 Photo Film 4 Patrone Main Body 5 Film Drawout 7 Perforation 8 Ridge 9 Protrusion 10 Hole 11 Cutout 12 Film Draw Path 13 Step 120 Photo Film Patrone 101 Spool 102 Photo Film 103 Patrone Main 104 Film outlet 104a Light-shielding member 106 Film tip 107 〃 108 Rib 102a Film innermost surface 201 Photo film Patrone 205 Photo film 206 Spool 206a Flange 206b Flange 206c Edge 207 Patrone body 208 Side plate 209 〃 208a Bearing 209a 208 209a 209b 〃 211 Telemp 212 Film entrance / exit 75 Spool 76 Photographic film 77a Ng 77b 〃 78 cartridge body 79a groove 79b 〃

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 3/00 C // B32B 27/36

Claims (10)

[Claims] 1. A silver halide photographic light-sensitive material containing a ferromagnetic fine powder in a transparent support, and having at least one silver halide emulsion layer on the support. Polyester film layer containing powder (A)
A silver halide photographic light-sensitive material characterized by being laminated by using a polyester film layer (B) containing no ferromagnetic fine powder. 2. At least one of the polyester film layer (A) and the polyester film layer (B) is made of polyester having a hydrophilic group, or contains polyethylene terephthalate as a main component mixed with a substance having water absorbability. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material comprises a polyester. 3. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein a laminate of the supports is formed by coextrusion. 4. The halogen according to claim 2, wherein the polyester having a hydrophilic group contains dibasic acid and glycol as main components, and the hydrophilic group is a hydroxy group, an alkylene oxide group or an ionic group. Silver halide photographic light-sensitive material. 5. The alkylene oxide group of the hydrophilic group is (poly) oxyethylene derivative, (poly) oxyglycerin derivative, and the ionic group is carboxylic acid derivative, sulfonic acid derivative, sulfinic acid derivative, sulfuric acid derivative, phosphoric acid. The silver halide photographic light-sensitive material according to claim 4, which is a derivative or a salt thereof. 6. The water-absorbing substance is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, a carboxylic acid group, or a salt thereof, a polyalkyleneoxy group, an alkoxy group, an alkoxycarbonyl group, a sulfamoyl group, or a carbamoyl group. The halogenated compound according to claim 2, which is a polymer having at least one functional group selected from the group consisting of groups, acylamino groups, sulfonamide groups, disulfonamide groups, ureido groups, urethane groups, alkylsulfonyl groups and alkoxysulfonyl groups. Silver photographic light-sensitive material. 7. The water-absorbing substance is an alkali metal,
Alkaline earth metal, Si, Al, Zr, Mo, Fe, S
3. A silver halide photographic light-sensitive material according to claim 2, which is a compound of at least one of oxides of b and Pb, sulfides, sulfates, sulfites, carbonates, hydroxides, halides and nitrates. .. 8. The ferromagnetic fine powder has a mean particle size of 0.04 μm to 3 μm selected from magnetic iron oxide, Co-containing magnetic iron oxide, ferromagnetic metal fine powder, and chromium oxide, and
4. The silver halide photograph according to claim 1, which is a needle-like ferromagnetic fine powder having a particle size ratio (major axis / minor axis) of 2 to 15 and is contained in an amount of 0.01 to 1 g per 1 m ^{2 of} the film. Photosensitive material. 9. The ferromagnetic fine powder has an average particle size of 0.04 to
A plate-shaped barium flight of 3μ, and 0.01 to 1 g per 1 m ^{2 of} film is contained.
~ 3 silver halide photographic light-sensitive material. 10. A spool provided rotatably in the cartridge body is rotated in the film feeding direction so that the tip of the silver halide photographic light-sensitive material wound on the spool is pulled out from the film outlet of the cartridge body. 2. A patrone system for a silver halide photographic light-sensitive material which is sent to the outside, which is used.
~ 9 silver halide photographic light-sensitive material.