JPH07134363A - Packaged body of photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain excellent scratching resistance and to prevent curling by specifying the void rate of a packaged body, using a polyester film as the supporting body containing one kind of aromatic dicarboxylic acids having metal sulfonate groups as the copolymer component and also containing a specified compd. CONSTITUTION:The void rate of the inside of the cartridge is <=0.25 defined by formula V=(B-A)/B. The supporting body is a polyester film containing aromatic dicarboxylic acids having metal sulfonate groups and one kind of compd. selected from among polyalkylene glycols and satd. fatty acid dicarboxylic acids as the copolymer component. Further, the photosensitive material has a layer containing a compd. selected from among compds. expressed by formulae I-IV. The supporting body is a multilayer polyester film having an asymmetric laminar structure on both sides on the center of thickness. The photosensitive material has a magnetic recording layer. The cartridge consists of synthetic plastics. In formula, A = (cross-sectional area of the rolled film) = (thickness) X (length) and B=(cross-sectional area of the cartridge).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material package, and more particularly to a small photographic light-sensitive material package.
The present invention relates to a photographic light-sensitive material package which is less likely to be charged with a photographic light-sensitive material even when the porosity in the cartridge is lowered, and which is also excellent in scratch resistance and curl eliminating property.

[0002]

2. Description of the Related Art At present, it is desired that a small camera, which is generally used in the general market, be further downsized. Usually, a film for photography is wound in a roll in a small camera, housed in a cartridge (patrone), and loaded. It is the most effective means to pursue the miniaturization of the camera to further miniaturize the cartridge and to make the storage space inside the camera compact.

To reduce the size of the cartridge, it is effective to reduce the thickness of the photographic film support. Since the polyethylene terephthalate film has a mechanical strength superior to that of the cellulose triacetate film, the thickness can be reduced.

However, when the cartridge is miniaturized, since the photographic film is tightly housed in the cartridge, the ratio of the voids in the container to the volume of the photographic film is reduced, and the photographic film is easily wound. Have When the curl becomes large, problems such as clogging and breaking of the film occur in the splicer processing machine and the like. Further, there is a problem that the curling is not sufficiently solved even after the development processing and the handling property is deteriorated.

Further, when the porosity in the cartridge is reduced, the film is in a state of being shrunk compared to the conventional case. Therefore, when the film is pulled out from the cartridge or rolled in, the front and back of the film are rubbed or the film is rubbed. There was a problem that the film itself was rubbed against the inside of the cartridge or the film outlet, and the film was scratched, which impaired the commercial value of the obtained photograph.

On the other hand, there has been proposed a method of recording various information on a photographic light-sensitive material by providing a magnetic recording layer on the photographic light-sensitive material.

For example, a stripe-shaped magnetic recording layer in which fine ferromagnetic particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and shooting conditions. JP-A-50-62627, JP-A-49-4503, US Pat. No. 3,243,376, JP-A-3,220,843 and the like, also, on the back surface of the photographic light-sensitive material, the amount of magnetic particles, size, etc. Providing a transparent magnetic recording layer having the required transparency by selection is described in US Pat. Nos. 3,782,947, 4,279,945 and 4,302,523. Also, U.S. Pat.No. 4,947,196, WO90
No. 04254 describes a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic substance that enables magnetic recording on the back surface of a photographic film.

When a camera having a magnetic head is used for inputting / outputting a magnetic signal, if the porosity in the cartridge is reduced and the photographic photosensitive material is easily charged due to friction or peeling, not only the conventional static problem but also static electricity It became a fatal problem that I / O error occurred due to the failure.

In order to solve such a problem, there has been conventionally known a method of providing a conductive layer containing various conductive substances on a photographic light-sensitive material.

Among such conductive layers, for example, Japanese Patent Publication Sho
The ionene type polymer as described in JP-A-57-56059 could not obtain a sufficient effect particularly under low humidity.

Further, it is known that the method of using a crystalline metal oxide as described in JP-A-56-143431 is effective because its conductivity does not depend on humidity. However, since such a crystalline metal oxide must be used in a large amount in order to obtain sufficient conductivity, it has a defect that the film is colored and the transparency is poor due to scattering.

Further, in such a crystalline metal oxide, fine cracks like cracks are generated in the layer containing the crystalline metal oxide, the transparency is impaired, the conductivity is deteriorated, and the layer containing the crystalline metal oxide is fragile and easily broken. When the porosity in the cartridge is reduced as described above, there is a problem that it does not have sufficient scratch resistance.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. A first object of the present invention is to provide a photographic light-sensitive material of a photographic light-sensitive material even when the void ratio in the cartridge is reduced due to the downsizing of the cartridge. A second object of the present invention is to provide a photographic light-sensitive material package having reduced chargeability, excellent scratch resistance, less tendency to curl, and excellent releasability thereof. It is an object of the present invention to provide a photographic light-sensitive material package in which the occurrence of magnetic signal input / output errors in a camera is reduced even if the porosity is reduced.

[0014]

The above object of the present invention is a photographic light-sensitive material package comprising a spool, a photographic light-sensitive material having one end locked to the spool and wound in a roll, and a cartridge body. The porosity V inside the cartridge represented by the following formula is 0.25 or less, the support of the photographic light-sensitive material is a polyester film, and the polyester film is an aromatic compound having a metal sulfonate group as a copolymerization component. A layer comprising a dicarboxylic acid and at least one selected from polyalkylene glycols and saturated fatty acid dicarboxylic acids, and having a layer containing a compound selected from the following general formulas [1] to [4] A photographic light-sensitive material package, wherein the support of the photographic light-sensitive material in the package is a multilayer film in which two or more layers made of polyester are laminated. That the laminated structure on both sides of the multilayer film is asymmetrical with respect to the position where the thickness of the multilayer film is divided into two parts, the photographic light-sensitive material of the package has a magnetic recording layer, and This is achieved by the packaging cartridge being made of synthetic plastic.

V = (B−A) / B where A = (film winding cross-sectional area) = (film thickness) × (film length) B = (cartridge internal cross-sectional area) = (cartridge Body sectional area)-(spool sectional area). or,

[0016]

[Chemical 5]

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

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

[0019]

[Chemical 6]

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

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[In the formula, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a lower alkyl group. L ₂ has an ionene chain 2
Represents a valent group, and L ₃ represents a monovalent group. A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Represent x _3, x ₄ is 0 to 20 mol%, y _3, y ₄ 0 to 70 mol%, z _3, z ₄ represents 30 to 100 mol%. The present invention will be described in detail below.

--Cartridge-- In the photographic light-sensitive material package of the present invention, the cartridge may be a system which is widely used at present, in which the tip of the photographic light-sensitive material is exposed outside the cartridge in advance, or U.S. Pat.Nos. 4,834,306, 4,84
No. 6,418, No. 4,832,275, etc., the tip of the photographic light-sensitive material is inside the cartridge in advance, and the spool around which the photographic light-sensitive material is wound is rotated in the opposite direction to the photographic light-sensitive direction. Any photographic photosensitive material packaging system may be used as long as the cartridge is a system for packaging the photographic photosensitive material as a whole, such as a system for sending the material out of the cartridge.

A void which is a free space inside the cartridge containing the photographic light-sensitive material is represented by a void ratio V represented by the following equation.

V = (B−A) / B (1) Here, A is the winding cross-sectional area of the film, and B is the cross-sectional area inside the cartridge, which are defined as follows.

A = (film thickness) × (film length) B = (cartridge body cross-sectional area)-(spool cross-sectional area) The unit is, for example, mm. 23 for all measurements
Perform at ℃ and 55% RH.

The thickness of the film is the total thickness of the photographic light-sensitive material, and is the total thickness of all the constituents such as the support, emulsion layer and backing layer.
It can be obtained by measuring the thickness at any 10 points with a TSU ELECTRONIC MICROMETER, etc.) and averaging.

The length of the film means the length of the portion housed in the cartridge. If the end of the film has been inserted into the spool, the end of the spool should be the one end.

The cross-sectional area of the body of the cartridge means the cross-sectional area of the inside of the cartridge in the cross section of the portion in which the film is accommodated, not the upper or lower end of the cartridge.
If there is a protrusion (rib) provided on the inside of the cartridge for the purpose of controlling the position of the film and improving sliding, the cross-sectional area inside the protrusion is adopted.

The cross-sectional area of the spool represents the cross-sectional area of the portion of the spool around which the film is wound.

The value of the porosity V is 0 <V ≦ 0.25, but 0.
It is more preferable that 04 ≦ V ≦ 0.22, and 0.08 ≦ V ≦ 0.
Most preferably it is 19.

To reduce the size of the camera, the cross-sectional area of the cartridge is preferably 370 mm ² or less, more preferably 28 mm ^2.
It is 5 mm ² or less. The sprue cross-sectional area is preferably 95 mm ² or less, more preferably 80 mm ² or less. The cartridge used in the present invention is mainly composed of synthetic plastic.

Examples of plastic materials include polystyrene, polyethylene, polypropylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, styrene-butadiene resin, methyl methacrylic resin, polyethylene phthalate, Teflon, nylon and the like. Among them, particularly preferable plastic materials are polystyrene, polyethylene, polypropylene and the like.

In forming the plastic, a plasticizer is optionally mixed with the plastic. 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.

Further, the cartridge is usually made of a plastic in which carbon black or the like is kneaded in order to impart a light shielding property.

The method of shielding the film withdrawal opening of the cartridge is arbitrary. A felt-shaped light-shielding member called "teremp" may be provided as in the past, and in the case of a system in which the leading edge of the film is stored in the cartridge in advance, it is necessary to form the film outlet so that it can be opened and closed. You may keep it in the closed state except the time.

The photographic light-sensitive material package of the present invention is generally stored in a sealed container.

As the sealed container, any container can be used as long as it can isolate the photographic light-sensitive material contained therein from the outside. Here, the term “isolation” refers to a state in which the outside air and the air inside the container do not substantially flow. Therefore, any container satisfying the above conditions can be used as a hermetically sealed container regardless of the material, shape and the like. For example, a container with a lid formed of a resin having low moisture permeability such as polyethylene, polypropylene, or polyvinyl chloride can be used. Also,
The cartridge itself can also be used as a hermetically sealed container with hermeticity. In the case of a system in which the leading edge of the photographic light-sensitive material is housed in the cartridge in advance, the cartridge does not have a sealing property, but the cartridge is moisture-proof film (polyethylene, polypropylene, polyvinyl chloride film, etc.). It is also possible to use a sealed container that is vacuum-sealed.

L ₂ and L ₃ in the general formulas [3] and [4] of the present invention are represented by the following general formulas [5], [6] and [7].
Those containing at least one kind of straight chain represented by are preferred.

[0041]

[Chemical 9]

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

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

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

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

Since actual n ₁ , n ₂ and n ₃ have distributions, they are represented by average values in the preferred compound examples. The distribution width depends on the compound.

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

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

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

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

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

[0052]

[Chemical 10]

[0053]

[Chemical 11]

[0054]

[Chemical 12]

[0055]

[Chemical 13]

[0056]

[Chemical 14]

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

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

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

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

The compounds of the general formulas [1] to [4] of the present invention may be contained in any layer of the photographic constitutional layers, but the protective layer of the photosensitive silver halide emulsion layer, the intermediate layer, the undercoat layer and the photosensitive layer. A back layer which is on the opposite side of the support from the photographic silver halide emulsion layer is more preferable, and the back layer is more preferable, and the back layer has a layer containing the compound of the present invention as a conductive layer, The recording layer preferably contains the compound of the present invention.

Next, the support will be described.

--Photographic Support-- The photographic support of the present invention has a polyester layer and / or a copolyester layer.

--Polyester-- The polyester as the material for forming the polyester layer is one having a repeating unit of a dicarboxylic acid and a diol as a main constituent, and preferably a repeating unit of an aromatic dibasic acid and a glycol. A polyester having a unit as a main constituent may be mentioned.

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

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

The preferred intrinsic viscosity of the polyester (measured at a temperature of 20 ° C. using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a weight ratio of 60:40) is not particularly limited, From the viewpoint of stretchability during film production, 0.45 to 0.80 is preferable, and 0.55 to 0.70 is particularly preferable.

--Copolymerized Polyester-- The copolymerized polyester used for forming the copolymerized polyester layer contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, and a repeating unit of a dicarboxylic acid and a diol. A main component, preferably a copolyester having an aromatic dibasic acid and a glycol as main components. Further, in the present invention, as the copolyester, a blended product of the copolyester and the polyester can also be mentioned.

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

The preferred intrinsic viscosity of the copolyester is not particularly limited, but is preferably 0.35 to 0.75 from the viewpoint of stretchability during the production of a laminated film, and particularly preferably 0.
45 to 0.65 is preferable.

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

[0078]

[Chemical formula 22]

The above-mentioned copolymerized polyester preferably contains a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid as a copolymerization component as long as the effects of the present invention are not impaired.

As the polyalkylene glycols, polyethylene glycol, polytetramethylene glycol and derivatives thereof are used. Among them, the polyethylene glycol represented by the formula (a) is preferable, and the molecular weight is not particularly limited, but is 300 to 20,000. Is preferred, more preferably 600 to 10000, especially 1000 to 5000
Those of are preferably used.

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

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

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

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

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

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

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

The polyester or copolymerized polyester for forming the film of the present invention may contain various additives. For example, a dye may be added to the polyester or copolymerized polyester for the purpose of preventing a light piping phenomenon (fogging) that occurs when light is incident from the edge of a photographic support coated with a photographic emulsion layer. . The type of this dye is not particularly limited, but those having excellent heat resistance are preferable in the film forming process, and examples thereof include anthraquinone chemical dyes. Further, as the film color tone, gray dyeing is preferable as seen in general light-sensitive materials,
You may mix and use 1 type or 2 or more types of dye.

-Layer Constitution of Film- The film of the present invention contains the polyester layer and / or the copolyester layer as described above, and any one of these has a two-layer structure, a three-layer structure or a four-layer structure. It has a laminated structure in which an arbitrary number of layers such as layers are laminated.
The "layer" constituting the film of the present invention has a thickness of 2 μm or more and is less than 2 μm.
For example, the subbing layer and the like are not regarded as "layers" constituting the film.

The polyester film support of the present invention is formed into a sheet through, for example, an extruder, a filter and a die which are controlled in a temperature range of 260 to 330 ° C. after sufficiently drying the polyester and / or the copolyester. Melt extrusion and cooling and solidification of the molten polymer on a rotating cooling drum give an unstretched film. After that,
It can be produced by biaxially stretching the unstretched film in the machine direction and the transverse direction and heat-setting.

Examples of the method for biaxially stretching the film include the following methods (A) to (C).

(A) A method in which an unstretched film is first stretched in the longitudinal direction, and then stretched in the transverse direction. (B) A method in which an unstretched film is stretched in the transverse direction first and then in the longitudinal direction. (C) Unstretched film. A method in which the film is stretched in the longitudinal direction in one stage or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction. The stretching is performed in order to satisfy the mechanical strength, dimensional stability, etc. of the polyester film support. , Area ratio 4-16
It is preferable to carry out in a double range.

The polyester film support of the present invention is a laminated layer in which a film or sheet formed by the above-mentioned method and a film or sheet made of another material by the coextrusion method or the laminating method and a film or sheet formed by the above-mentioned method are laminated. It is a structure. The obtained polyester film support is particularly suitable as a support for a photographic film used in a roll form.

The thickness of the polyester film support is not particularly limited, and any thickness can be used depending on the application, but it is preferably 125 μm or less, more preferably
The thickness is 50 to 115 μm, more preferably 65 to 100 μm.

In the present invention, the curl of the support is preferably curled concavely in the width direction on the back layer side,
More preferably, in 1 / R display, -5 to -35 (1 / m)
Is the range. However, R is the radius of curvature of the film, the unit is m, and the case of curling on the side having the emulsion layer is indicated as +.

On the polyester film support of the present invention,
As a method of previously providing a curl in the width direction, in the case of a two-layer structure, it is preferable that the two layers forming the film are composed of a polyester layer, and the thickness may be the same or different. Preferably the polyester species of the upper and lower layers of the laminated film is the main constituent component, or
It is preferable that the amounts of the main constituents are different, or the amounts of the copolymerization components or the copolymerization components are different. For example, it is not particularly limited, but may be composed of a polyester layer and a copolyester layer, or a copolyester layer and a copolyester layer. The copolymerization component preferably contains an aromatic dicarboxylic acid having a metal sulfonate group, and further,
It is preferable to contain polyalkylene glycol and / or saturated aliphatic dicarboxylic acid. In this case, as a copolymerization component in the copolymerized polyester used, an aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 2 to 7 mol% based on all ester bonds, and polyalkylene glycols are further used as a copolymerization component. And / or saturated aliphatic dicarboxylic acid in an amount of 3 to 3 with respect to the total weight of the copolymerization component.
It is particularly preferable to contain 10% by weight. When it is composed of two layers, a curl in the width direction can be imparted to the laminated film by appropriately adjusting the above items.

In the case of a three-layer structure, it is preferable that the two outer layers are composed of polyester layers. However, if the central layer is a polyester layer as long as the effects of the present invention are not impaired, other materials such as polycarbonate are not particularly limited. , Polyether, polyamide, polyimide, polyphthalamide, polyphthalimide and the like. It is preferable that all three layers are polyester layers. As the layer structure, it is preferable that the outer layers have different thicknesses, and when the thickness of each of the outer layers is d _A and d _B from the thickest one, the ratio d _A / d _B is not particularly limited. Is 1.1 ≦ d _A / d _B ≦ 5, preferably 1.3 ≦ d _A / d
_B ≦ 3. In the case of a three-layer structure, the thickness of the outer layer may be the same or different, but the polyester species of the upper and lower layers which are the outer layers of the laminated film are the main constituent components, or
It is preferable that the amounts of the main constituents are different, the amounts of the copolymerization components or the copolymerization components are different, and further, the intrinsic viscosities are different. In this case, as a copolymerization component in the copolymerized polyester used, an aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 2 to 7 mol% based on all ester bonds, and polyalkylene glycols are further used as a copolymerization component. It is particularly preferable to contain 3 to 10% by weight of the saturated aliphatic dicarboxylic acid with respect to the total weight of the copolymerization component. When it is composed of three layers, the widthwise curl can be imparted to the laminated film by appropriately adjusting the above items. Intrinsic viscosity difference ΔIV is 0.02 to 0.
5, preferably 0.05 to 0.4, particularly preferably 0.1 to 0.3.

In addition, in the case of the above-mentioned two-layer, three-layer, and the constitution of four or more layers, what is necessary for imparting a width curl to the film of the present invention is that the total thickness of the film is A width curl can be imparted to a surface divided in half if the layer structure is asymmetrical above and below the surface.

The asymmetry referred to here is not particularly limited, but for example, the order of forming the polyester layer or the layer made of another material, the thickness of the polyester layer or the layer made of another material, and the upper and lower sides of the half-divided surface. It also includes that the amount of the main constituent component of the polyester species is different, that the amount of the copolymerization component or the amount of the copolymerization component is different, and that the intrinsic viscosity is different.

As a method for measuring the asymmetry of these laminated films, various analytical instruments can be used.
Although not particularly limited, the cross-section of the film can be observed under a microscope and a micrograph can be taken regarding the layer structure. In addition, while observing the film under a microscope, each layer is scraped off, or the film is divided into halves, and each of the upper and lower layers is scraped from the upper and lower sides to obtain an analyte.
Hydrolysis and liquid chromatography or NMR
It may be measured by various measuring devices such as the like, or the inherent viscosity may be measured by NMR, GPC (gel permeation chromatography) or the like after the analyte is dissolved in a solvent, or the analyte may be powdered as it is. It is possible to measure IR (infrared spectroscopic instrument) etc. by mixing with X-ray spectroscopic instrument or KBr etc., and as a result, absolute amount or asymmetry in the difference in peak position, intensity etc. of the measurement result corresponding to it. Can be measured.

When the film of the present invention has a two-layer laminated structure, in the case of a polyester layer and a copolyester layer, the copolyester layer side usually has a concave curl in the width direction, and the copolyester layer. In the case of the two, the curl in the width direction can be adjusted by appropriately adjusting the film thickness and the composition amount. In the case of a three-layer structure, when the outer layer is a copolyester layer, the above-mentioned d _A side can usually impart curl in the width direction of the concave surface, and the film of the present invention has two layers, three Even if it is a layer, four layers or more, it is not limited to these, and a width curl is appropriately provided by appropriately adjusting the above-mentioned items such as the layer constitution, the film thickness and the amount of the copolymerization component of the present invention. can do.

Next, the magnetic recording layer will be described.

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

Methods for producing these magnetic powders are known,
The magnetic powder used in the present invention can also be manufactured according to a known method.

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

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

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

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

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

If the particle size of the magnetic particles is made smaller than a certain level, the required magnetic properties cannot be obtained. Therefore, it is preferable to make the particle size of the magnetic powder small within the range where the required magnetic characteristics are obtained. Further, if the coating amount of the magnetic particles is reduced to a certain extent or more, the required magnetic characteristics cannot be obtained, so it is preferable to reduce the coating amount within the range where the required magnetic characteristics are obtained.

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

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

The thermoplastic resin has a Tg of -40 ° C to 150 ° C.
C., preferably 60.degree. C. to 120.degree. C., with a weight average molecular weight of 10,000 to 300,000, more preferably 50,000 to 200,000.

The above binder may have a polar group in its molecule.

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

Examples of the hydrophilic binder usable in the present invention include Research Disclosure No. 17643,
Water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters described on page 26, and No. 18716, page 651 can be mentioned. Most preferred is gelatin.

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

The hydrophilic binder containing gelatin is preferably hardened. Hardeners that can be used include aldehyde compounds, ketone compounds, reactive halogen-containing compounds, reactive olefin-containing compounds, N-
Hydroxymethylphthalimide, N-methylol compound,
Isocyanates, aziridine compounds, acid derivatives,
Examples thereof include epoxy compounds and halogen carboxaldehydes. Also, an inorganic hardener may be used.

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

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

In the case of forming an optically transparent magnetic recording layer, the binder is preferably used in an amount of 1 to 20 parts by weight based on 1 part by weight of the magnetic powder. More preferably, it is 2 to 15 parts by weight with respect to 1 part by weight of the magnetic powder. Further, the solvent is used in such an amount that the coating can be easily performed.

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

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

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to provide the magnetic recording layer with functions such as imparting lubricity, preventing electrification, preventing adhesion, and improving friction and abrasion characteristics. Various additives such as agents can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and for preventing clogging of the magnetic head. Abrasives can be added.

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

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

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

The silver halide emulsion used in the present invention is, for example, Research Disclosure (RD) No. 17643, 22.
Page 23 (December 1978) “I. Emulsion prepar
a-tion and types) ”and the same (RD) No.18716,648
P.Glafkides, Chemic et Phisique Photographiqu
e, Paul Montel, 1967) "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsi
on Chemistry, Focal Press 1966), "Photoemulsion production and coating" by Zelikmann et al., published by Focal Press (VL
Zelikman et al, Making and Coating Photographic Emu
lsion, Focal Press, 1964) and the like.

Emulsions are described in US Pat. Nos. 3,574,628 and 3,6.
The monodisperse emulsions described in 65,394 and GB 1,413,748 are also preferred.

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

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

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

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

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

In the case of constituting a color photographic light-sensitive material, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in RD308119 VII-K can be adopted.

In order to firmly adhere these photographic constituent layers (eg, photosensitive silver halide emulsion layer, intermediate layer, filter layer, magnetic recording layer, conductive layer) to the support, an undercoat layer is provided on the support. It may be provided, or the support may be treated with a chemical,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment,
Surface activation treatment such as high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment, ozone oxidation treatment may be performed. Further, an undercoat layer may be provided after the surface activation treatment, and a photographic emulsion layer may be coated thereon.

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

[0138]

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

Example 1 A. Production of polyester film support (Preparation of support 1) 100 parts by weight of dimethyl terephthalate,
64 parts by weight of ethylene glycol and 0.1 part by weight of hydrate of calcium acetate as a transesterification catalyst were added,
The transesterification reaction was carried out by a conventional method.

The product obtained is treated with 5-sodium sulfo-
Di (β-hydroxyethyl) isophthalic acid (abbreviation; SI
P) 28 parts by weight of ethylene glycol solution (concentration 35% by weight), and polyethylene glycol (abbreviation: PEG)
(Number average molecular weight: 3000) 8.1 parts by weight was added, and then
Antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.13 part by weight, Irganox 1010 as an antioxidant
(CIBA-GEIGY) 0.2 parts by weight and sodium hydroxide
0.02 part by weight was added. Then gradually raise the temperature and reduce the pressure,
Polymerization was performed under the conditions of 280 ° C. and 0.5 mmHg to obtain a copolyester M ₁ having an intrinsic viscosity of 0.55.

A photographic support was obtained in the following manner using the copolymerized polyester (M ₁ ) and photographic polyethylene terephthalate (P) (inherent viscosity: 0.65) used as the polyester layer.

Copolyester (M ₁ ) and polyethylene terephthalate (P) were each vacuum dried at 150 ° C., and then melt extruded at 285 ° C. using three extruders, and the emulsion layer coating side of the support was used. From the above, the layers were joined in a T-die in a layered manner so that the thickness ratio of the copolyester (M ₁ ) / polyethylene terephthalate (P) / copolyester (M ₁ ) was 1: 2: 3, and then on the cooling drum. Then, it was rapidly solidified by cooling to prepare a polyester laminated unstretched film. This laminated unstretched film was stretched at 85 ° C in the vertical direction by 3.5
After being double-stretched and further stretched 3.5 times in the transverse direction at 95 ° C., it was heat-set at 210 ° C. to obtain a polyester film support 1 having a thickness of 90 μm.

Both sides of the support 1 were subjected to a corona discharge treatment of 8 W / (m ² · min), and the subbing coating solution B-1 was applied to a thinner outer layer of the copolyester layer of the support to give a dry film thickness of 0.8. to form a subbing layer B-1 on the other side of the support, and the subbing coating solution B-2 shown below is applied to the other surface of the support to a dry film thickness of 0.8 μm. B-2 was formed.

<Undercoating Liquid B-1> Copolymer latex liquid (solid content: 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight, and 2-hydroxyethyl acrylate 25% by weight). 30%) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating liquid B-2> 40 wt% butyl acrylate, 20 wt% styrene and Glycidyl acrylate 40% by weight copolymer latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml Further undercoat layer B -1 and 8 W / (m on the undercoat layer B-2
² min. Of corona discharge, and on the undercoat layer B-1,
The undercoat layer B-3 is formed by applying the following coating liquid B-3 to a dry film thickness of 0.1 μm, and the undercoat layer B-2 has the following coating liquid B-4 on the dry film thickness. The undercoat layer B-4 having an antistatic function was formed by coating so as to have a thickness of 0.1 μm.

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

<MC-1> The following components were mixed together by a dissolver and then dispersed by a sand mill to obtain a dispersion liquid.

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

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml Further, a corona discharge of 25 W / (m ² · min) was applied on the undercoat layer B-3 to sequentially form the following photographic constituent layers. A multilayer color photographic light-sensitive material was prepared.

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

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

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

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

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

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

(Formation of External High Iodity Phase-Shell Phase-) Subsequently, while maintaining at pHAg10.1 and pH6.0, (H-2) and (S
-2) and were added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

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

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

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

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

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

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

[0162]

[Chemical formula 23]

[0163]

[Chemical formula 24]

[0164]

[Chemical 25]

[0165]

[Chemical formula 26]

[0166]

[Chemical 27]

[0167]

[Chemical 28]

[0168]

[Chemical 29]

[0169]

[Chemical 30]

[0170]

[Chemical 31]

[0171]

[Chemical 32]

[0172]

[Chemical 33]

[0173]

[Chemical 34]

The total thickness of the silver halide photographic light-sensitive material was 120 μm.

C. Preparation of package for photographic light-sensitive material A silver halide photographic light-sensitive material formed by coating <Back layer> and <Emulsion layer> on support 1 was slit into a width of 35 mm, cut into 118 cm, and the size shown in Table 1 Samples 001 to 025 of photographic light-sensitive material packages with different porosities were prepared by winding the cartridge in full length. As for the cartridge, the L type is a current equivalent size, and the MP types are miniaturized sizes.

[0176]

[Table 1]

(Evaluation Method) The photographic light-sensitive material package samples 001 to 025 prepared as described above were evaluated as described below, and the results are shown in Table 2.

<Scratch resistance> After fixing the cartridge and pulling it out parallel to the photographic film outlet at 10 cm / sec, the film was wound into the cartridge and again 10 cm / sec.
The film was pulled out at sec, and the surface of the film back layer was visually evaluated and represented by the following grades.

⊚: No scratches were found. ◯: 5 or less fine scratches were found per line. ×: 6 or more fine scratches were found per line and / or 1 over the entire length. More than a bunch of scratches were generated << Reproduction error >> A camera having a magnetic head described in U.S. Pat. No. 4,947,196 was made so that each of cartridges L to P could be inserted.

On the other hand, the tracks C0 to C are preliminarily input to the film by the signal input method described in the specification in the photographic photosensitive material manufacturing process.
I wrote a signal to 3.

In FIG. 1, 101 is a perforation,
F00 to F29 represent tracks for recording magnetic information, like the tracks C0 to C3.

This film was passed through a camera having the above-mentioned reproducing head at 23 ° C. and 10% RH, and a reproduction output error was examined. The reproduction output error means that the average reproduction output per track has no electrostatic noise and is 70% or less of the reproduction output when the head accurately contacts the film. 20 samples were tested for each sample and the number of films in which a reproduction output error occurred was counted.

<< Turbidity >> The sample was subjected to the following development treatment without being exposed, and the turbidity was measured using a Poic integrating sphere hygrometer SEP-PT-501D type manufactured by Mitsubishi Kasei. <Development processing> 1. Color development ・ ・ ・ 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleaching ... 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Washing with water ・ ・ ・ ・ 3 minutes 15 seconds 24-41 ℃ 4. Settling ··· 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water ... 3 minutes 15 seconds 24-41 ° C 6. Stability ・ ・ ・ ・ 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying ... 50 ° C or less The composition of the processing liquid used in each step is shown below.

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

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

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

[0187]

[Table 2]

Here, Comparative Compound A; average particle size 0.2 μ, volume resistivity 1 × 10 ² Ω
Tin oxide powder

[0189]

[Chemical 35]

It is

As is clear from Table 2, the samples of the present invention are excellent in scratch resistance even when the cartridges M to P suitable for miniaturization of the camera are used, that is, when the porosity is 0.25 or less. It turns out that there is no error and it is excellent.

It is also understood that when the compound of the present invention is used, the turbidity after the development processing is small and the transparency is excellent.

On the other hand, when an L size cartridge (current type) is used, that is, when the porosity is larger than 0.25, the scratch resistance is excellent and no error occurs, but it is not suitable for downsizing the camera.

Example 2 (Preparation of Support) As the support of the present invention, in addition to the support 1 prepared in Example 1, the film thickness ratio of three layers was M ₁ : P: M ₁ =
Made in the same manner as Support 1 except that it was 1: 1: 1
The support 2 of 90 μm and the copolyester (M ₁ ) were vacuum dried at 150 ° C. and then 285
Melt extrusion was performed at 0 ° C., and rapid cooling and solidification was performed in a cooling drum shape to prepare a polyester unstretched film. This unstretched film was stretched 3.5 times in the machine direction at 85 ° C, and then in the transverse direction at 95 ° C.
After stretching 3.5 times, it was heat set at 210 ° C. to prepare a support 3 having a thickness of 90 μm.

As the support 4, a polyethylene terephthalate thickness of 90 μ was prepared.

(Preparation of Photosensitive Material) Undercoat layer B-2 and conductive layer B are provided on the back layer side in the same manner as in Example 1 except that MC-1 is not coated on the supports 1 to 4 thus prepared. -4 (Compound P-1 of the present invention, 0.07 g / m ² ) and OC-1 were sequentially applied.

Further, undercoat layers B-1 and B-3 were coated on the other surface of the support to further form a photographic constituent layer.

The total thickness of the silver halide photographic light-sensitive material was 119μ.

This silver halide photographic material was used in Example 1.
In the same manner as described above, the photographic photosensitive material package was prepared by being wound into L to P cartridges.

(Evaluation Method) Table 3 shows the results of evaluation of the photographic light-sensitive material package sample Nos. 31 to 50 prepared as described above. The scratch resistance was evaluated in the same manner as in Example 1.

<Static Mark Occurrence> The unexposed package sample was conditioned at 23 ° C. and 10% RH for 24 hours, then passed through the camera under the same air conditioning conditions, and then subjected to the development treatment shown in Example 1. Then, the degree of occurrence of static marks was examined and evaluated according to the following criteria.

A: No generation of static marks was observed at all. B: 〃 Slightly recognized C: 〃 Significantly recognized D: 〃 Almost all the surface was observed. << Splicer suitability / unwinding property >> Sample 23 ℃, 55%
Film splicer processor (PS-35-2:
After connecting with Noritsu Koki Co., Ltd., the film was developed normally by an automatic film processor (NCV60: Noritsu Koki Co., Ltd.).

--Aptitude of Splicer-- The following three grades were evaluated. In practical use, clogging and breaking of the film in the film splicer processor should never occur, and a grade of O or higher is required.

⊚: No clogging or breakage was observed. ○: No clogging or breakage was observed, the leading edge of the film was slightly difficult to enter. ×: Clogging or breakage was observed. In the atmosphere of 55 ° C. and 55% RH, the outside of the film was grabbed and hung, and the humidity was controlled for 1 day. The length of the portion 12 cm from the tip corresponding to the core when naturally hanging was measured, the ratio to the original length was obtained, and the evaluation was made in the following three stages.

In terms of the performance of the photographic film, a grade of O or higher is preferable.

◎: 70% or more ○: 50% to 70% ×: less than 50%

[0207]

[Table 3]

As is apparent from Table 3, the sample of the present invention has improved curl, is excellent in splicer suitability, and is excellent in curl canceling property as compared with the comparative sample. Further, when the support 4 is used, static marks are easily generated even when the compound of the present invention is used.

[0209]

According to the present invention, the chargeability of the photographic light-sensitive material is reduced and the scratch resistance is excellent, especially when the void ratio in the cartridge is reduced due to the miniaturization of the photographic light-sensitive material package. It is possible to provide a photographic light-sensitive material package which is less likely to have a curl and is excellent in eliminating it.

[Brief description of drawings]

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

[Explanation of symbols] 101 Perforation C0 to C3 tracks (record magnetic information) F00 to F29 tracks (record magnetic information)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/795 1/81 1/89

Claims (5)

[Claims] 1. A photographic light-sensitive material package comprising a spool, a photographic light-sensitive material having one end locked to the spool and wound into a roll, and a cartridge body, wherein the cartridge has the following formula: The porosity V is 0.25 or less, the support of the photographic light-sensitive material is a polyester film, and the polyester film has, as a copolymerization component, an aromatic dicarboxylic acid having a metal sulfonate group, a polyalkylene glycol and a saturated fatty acid. Containing at least one selected from dicarboxylic acids,
A photographic light-sensitive material package having a layer containing a compound selected from the following general formulas [1] to [4]. V = (B−A) / B where A = (film winding cross-sectional area) = (film thickness) × (film length) B = (cartridge internal cross-sectional area) = (cartridge body cross-sectional area) )-(Spool cross-sectional area). In addition, [Wherein R ₁ represents a hydrogen atom or a lower alkyl group,
R ₂ , R ₃ and R ₄ are each an alkyl group, an aralkyl group,
Represents an alkenyl group and an allyl group. R ₂ , R ₃ and R ₄ may be the same or different. _{Two of} R ₂ , R ₃ and R ₄ may be connected to form a 5-membered ring or 6-membered ring together with the nitrogen atom. L ₁ represents a divalent group. X ₁ represents an anion. x ₁ , y ₁ and z ₁ represent a mole fraction, x ₁ is 0 to 20%,
y ₁ is 0 to 70% and z ₁ is 30 to 100%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain,
B represents a repeating unit having a copolymerizable ethylenically unsaturated group. ] [Chemical 2] [In the formula, R ₅ represents a hydrogen atom or a lower alkyl group, and R ₆
Represents an alkyl group, an alkenyl group, an aralkyl group, and an allyl group. D is a 5- or 6-membered heterocyclic ring having one or two nitrogen atoms. D may have a substituent. X ₂ represents an anion. x ₂ , y ₂ and z ₂ represent mole fractions, x ₂ is 0 to 20%, y ₂ is 0 to 70%, and z ₂ is 30 to 100%.
%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Indicates a unit. ] [Chemical 3] [Chemical 4] [In the formula, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a lower alkyl group. L ₂ represents a divalent group having an ionene chain,
L ₃ represents a monovalent group. A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Represent
x ₃ and x ₄ are 0 to 20 mol%, y ₃ and y ₄ are 0 to 70 mol%, z
₃ , z ₄ represents 30 to 100 mol%. ] 2. The photographic light-sensitive material package according to claim 1, wherein the support of the photographic light-sensitive material is a multilayer film in which two or more layers made of polyester are laminated. 3. The photographic light-sensitive material package according to claim 2, wherein the laminated structures on both sides of the multilayer film are asymmetrical with respect to a position where the thickness of the multilayer film is divided into two equal parts. 4. The photographic light-sensitive material package according to claim 1, wherein the photographic light-sensitive material has a magnetic recording layer. 5. The photographic light-sensitive material package according to claim 1, wherein the cartridge is made of synthetic plastic.