JPH0643582A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material which is extremely ameliorated in pressure fogging and is free from the permanent set of winding when the material is housed into a small-sized cartridge. CONSTITUTION:This silver halide photographic sensitive material is housed into a cartridge to <=10mm core diameter of the spool therein. The base of the above-mentioned silver halide photographic sensitive material is polyester having >=90 deg.C glass transition temp. In addition, at least one layer of the silver halide emulsion thereof contain flat planar particles at >=20% (weight) in the entire emulsion layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material or a light-sensitive material) to be housed in a small-diameter cartridge, and particularly when it is wound into a roll. The present invention relates to a silver halide photographic light-sensitive material having significantly improved pressure fog.

[0002]

2. Description of the Related Art Currently, negative and reversal photographic film cartridges that are in widespread use have a core diameter of 11.5 at the center.
It has a spool of mm and an outer diameter of 26 mm. However, the patrone generally has the longest roll of the photosensitive material for taking 36 sheets, and a sufficient space exists in the patrone. On the other hand, in the field of photography, downsizing has been eagerly pursued, but downsizing of cameras and the like is almost at the limit. Therefore, in order to further reduce the size of the camera or the like, it is possible to reduce the size of the existing cartridge (abbreviated as 135 size) that accommodates the sensitive material. For this reason, it has been achieved by reducing the outer diameter (for example, 21 mm or less) and reducing the thickness of triacetyl cellulose as a support (122 → 115 μm), and it has been introduced to the market as a film with a lens.
Certainly, this method has made it possible to make the camera smaller in appearance and to make the camera smaller. However, this method has a serious problem that the number of photographed images is limited to 24 and the number of photographed images cannot be stored. This can be achieved by reducing the thickness of the photosensitive material (particularly the thickness of the support) or reducing the spool. However, when the currently used triacetyl cellulose support is made to have a thickness of 115 μm or less, the strength of the support is greatly deteriorated and the support is damaged during handling.

Therefore, instead of triacetyl cellulose, polyethylene terephthalate (PE
The thickness can be reduced by introducing T), for example, 90 μm.
The support can be used without any trouble in handling. By using this PET with an outer diameter of 21 mm and a spool diameter of 7 mm, 36 shots can be stored. However, although it has become possible to use PET to make a compact patrone that can accommodate a large number of rolls, it has been found that a new fatal problem occurs. That is, when stored at a high temperature, for example, 80 ° C for 2 hours (this is
Under conditions that can occur during the summer day of a car with the door closed), the roll-shaped curl is very strong, and it is not conveyed smoothly during development processing with the Minilab automatic processor after shooting and the core of the core part Development unevenness and breakage occurred and the image was greatly impaired. Therefore, US Pat. No. 4,141,7
It is stated that the polyester described in No. 35 is preheated to improve the curl. Although this method improves the curling habit, it has been a problem that fog caused by the winding pressure occurs during storage because the sensitive material is rolled into a small cartridge. In particular, the fog on the winding core of the small diameter spool was extremely bad.

[0004]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a light-sensitive material having a small pressure fog over time of the light-sensitive material wound in a roll on a small diameter spool.
It is a second object of the present invention to provide a sensitive material which is excellent in transportability in a minilab because the sensitive material wound in a roll on a small-diameter spool does not tend to curl even when stored at high temperature.

[0005]

These objects of the present invention are to support a silver halide photographic light-sensitive material in a silver halide photographic light-sensitive material in which a core diameter of a spool in a cartridge is 10 mm or less. The polyester having a glass transition point of 90 ° C. or higher, and at least one silver halide emulsion layer comprises tabular grains in an amount of 20% of the total emulsion.
This can be achieved by a silver halide photographic light-sensitive material characterized by containing at least 100% by weight. First, a description will be given of the curl measurement method used thereafter and terms related thereto. (1) Core set Wrap the film around the spool to create a curl (2) Core set curl (curl value) The curl in the length direction applied by the core set. The degree of curling was measured in accordance with Test Method A of ANSI / ASC PH 1.29-1985 and expressed as 1 / R _m (R is the curl radius). (3) Absolute core set curl This is the core set curl of photographic film before the curl is improved. (4) Controlled core set curl This is the core set curl of the photographic film after the curl has been improved. (5) True core set curl (absolute core set curl)-(Controlled core set curl) (6) Curl reduction rate (true core set curl / absolute core set curl) x 1
00 (7) Glass transition temperature (Tg) Using a differential thermal analyzer (DSC), sample film 10
When an endothermic peak appears in the arithmetic mean temperature or Tg of the temperature at which deviation starts from the baseline and the temperature at which the baseline returns to a new baseline when mg is heated in a helium-nitrogen stream at 20 ° C / min. The temperature showing the maximum value of the endothermic peak is defined as Tg.

The present invention will be described in detail below. The cartridge of the present invention is characterized in that the spool has a core diameter of 10 mm to 4 mm, more preferably 9 mm to 4 mm, still more preferably 8 mm to 4 mm. Also, 8
Core diameters of mm to 5 mm are particularly preferred. At this time, the outer diameter of the cartridge can be reduced by setting the core diameter to, for example, 7 mm.
2 μm) 24 for an outer diameter 21 mm thin cartridge
Holds up to 3 sheets, and 3 for PET support (thickness 90 μm)
Only 6 sheets can be stored, but the support polyethylene naphthalate (PEN, thickness 80 μm) of the present invention can store up to 40 sheets of the current size. As described above, in the cartridge of the present invention in which the spool diameter is reduced, the outer diameter can be greatly reduced by making the support thin.
Next, the polyester of the present invention having a glass transition temperature of 90 ° C. or higher will be described. These polyesters are synthesized with a dicarboxylic acid (dibasic acid) and a diol as main components.
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, tetrachlorophthalic anhydride,
3,6-endomethylenetetrahydrophthalic anhydride,
1,4-cyclohexanedicarboxylic acid,

[0007]

[Chemical 1]

[0008]

[Chemical 2]

And the like. Usable diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 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, resorcin, hydroquinone, 1,4
-Benzenedimethanol,

[0010]

[Chemical 3]

[0011]

[Chemical 4]

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

[0013]

[Chemical 5]

Among the polyesters composed of these diols and dicarboxylic acids, more preferred are polyethylene, 2,6-dinaphthalate (PEN), polyacrylate (PAr), polycyclohexanedimethanol terephthalate (PCT) and the like. Homopolymer and dicarboxylic acid 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), paraphenylenedicarboxylic acid (PPDC) ), As a diol, ethylene glycol (EG), cyclohexanedimethanol (CHD
M), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), and parahydroxybenzoic acid (PHB) as a hydroxycarboxylic acid.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) is copolymerized. More preferred among these are naphthalene dicarboxylic acid, terephthalic acid and ethylene glycol copolymers (mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 and 1.00, 0.
It is more preferably 5: 0.5 to 0.8: 0.2. ), A copolymer of terephthalic acid, ethylene glycol, and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, more preferably 0.5: 0.5). .About.0: 0.9), isophthalic acid, paraphenylenedicarboxylic acid, and a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0.1 when terephthalic acid is 1). 10.
0, 0.1 to 20.0, and more preferably 0.
2 to 5.0, preferably 0.2 to 10.0), naphthalene dicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.7: 0. 3 is preferable, and more preferably 0.9: 0.1 to 0.6: 0.
4) Copolymer of terephthalic acid, ethylene glycol and biphenol (The molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1: 0.9 to 0. 7: 0.3), a copolymer of para-hydroxybenzoic acid, ethylene glycol and terephthalic acid (molar ratio of para-hydroxybenzoic acid, ethylene glycol is 1: 0 to 0.1 :).
0.9 is preferable, and 0.9: 0.1 is more preferable.
0.2: 0.8) and other copolymers and PEN and PET
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable, and 0.
5: 0.5 to 0.8: 0.2 is more preferable), PET
And PAr (composition ratio of 0.6: 0.4 to 0: 1.0 is preferable, and 0.5: 0.5 to 0: 0.9 is more preferable).

PEN is the most balanced of these polyesters, has a mechanical strength, especially a high elastic modulus, and has a glass transition temperature of about 120 ° C., which is sufficiently high.
However, it has the drawback of emitting fluorescence. On the other hand, P
CT has a high mechanical strength and a glass transition temperature as high as around 110 ° C., but has an extremely high crystallization rate, and has a drawback that it is difficult to obtain a transparent film. PAr has the highest glass transition temperature (190 ° C.) of these polymers, but has a drawback that mechanical strength is weaker than that of PET. Therefore, in order to make up for these drawbacks, blends of these polymers or copolymers of the monomers forming them can be used. These homopolymers and copolymers can be synthesized according to conventionally known polyester production methods. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, it can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, using a transesterification reaction, a catalyst or a polymerization reaction catalyst,
A heat resistance stabilizer may be added. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103 to 136, "Synthetic Polymer V" (Asakura Shoten, 1971). Year)
It can be performed with reference to the description on pages 187 to 286. The preferred average molecular weight range for these polyesters is about 10,000 to 500,000.

Polymer blends of the polymers thus obtained are disclosed in JP-A-49-5482 and JP-A-64-5482.
4325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779.
-82, 294, 807-14, it can be easily formed.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Example of polyester compound Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. PCT: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) ) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Copolymer (() represents a molar ratio.) PBC-12 , 6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. PBC-2 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. PBC-3 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. PBC-4 TPA / EG / BPA (100/50 50) Tg = 105 ° C. PBC-5 TPA / EG / BPA (100/25/75) Tg = 135 ° C. PBC-6 TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. PBC- 7 IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C. PBC-9 TPA / EG / BP (100 / 20/20) Tg = 115 ° C. PBC-10 PHBA / EG / TPA (200/100/100) Tg = 125 ° C. Polymer blend (() represents weight ratio.) PBB-1 PEN / PET (60 / 40) Tg = 95 ° C. PBB-2 PEN / PET (80/20) Tg = 104 ° C. PBB-3 PAr / PEN (50/50) Tg = 1 2 ° C. PBB-4 PAr / PCT (50/50) Tg = 118 ° C. PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 ℃

All of the above polyesters have a flexural modulus higher than that of TAC, and it is possible to realize the original purpose of thinning the film. However, PEN has the strongest bending elasticity among these, and by using this, it is possible to reduce the film thickness required from 122 μm for TAC to 80 μm. The thickness of these polymer films is 50 μm or more and 300 μm or less.
At 50 μm or less, a transparent polymer film having bending elasticity capable of withstanding the contraction stress of the photosensitive layer has not yet existed, and at 300 μm or more, there is no point in using a fine spool. Further, an ultraviolet absorber may be kneaded into these polymer films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the amount thereof added is usually 0.5% by weight to 20% by weight based on the weight of the polymer film.
%, Preferably about 1 to 10% by weight. If it is less than 0.5% by weight, the effect of suppressing the deterioration of ultraviolet rays cannot be expected. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4. Benzophenone-based compounds such as 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2
(2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy 3 ', 5'-di-t-
Examples include benzotriazole-based UV absorbers such as butylphenyl) benzotriazole, 2 (2′-hydroxy-3′-di-t-butyl-5′-methylphenyl) benzotriazole, salicylate-based UV absorbers such as phenyl salicylate and methyl salicylate. To be

Further, one of the properties which poses a problem when the polyester film is used as a support for a photographic light-sensitive material is a problem of fogging caused by the high refractive index of the support. Polyesters, especially aromatic polyesters, have a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated thereon, has a refractive index of 1.50 to 1.55. Less than this value. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase the film haze. The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye has excellent heat resistance in the film forming temperature range of the polyester film, and polyester Those having excellent compatibility with are preferable. From the above viewpoints, as the dye, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be imparted with slipperiness depending on the application, and the slipperiness imparting means is not particularly limited.
The kneading of an inert inorganic compound or the coating of a surfactant is used as a general method. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC.
Examples are O ₃ , talc, kaolin and the like. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system described above, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material. Therefore, in the slipperiness imparting method means, a polyester film is used as an external particle system. It is desirable to select SiO ₂ having a refractive index relatively close to that, or an internal particle system capable of relatively reducing the precipitated particle size. Furthermore, in the case of imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

When these polyester films (polymer films) of the present invention are used for a support, since each of these polymer films has a hydrophobic surface, a photograph consisting of a protective colloid mainly containing gelatin is provided on the support. A layer (for example, a photosensitive silver halide emulsion layer, an intermediate layer,
It is very difficult to firmly bond the filter layer). The conventional techniques attempted to overcome such difficulties are (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment. , A method of surface activation such as mixed acid treatment, ozone oxidation treatment, etc., and then directly applying a photographic emulsion to obtain the adhesive force, and (2) after these surface treatments once or without surface treatment, There are two methods: a method of providing an undercoat layer and a method of coating a photographic emulsion layer on the undercoat layer. (For example, U.S. Pat. Nos. 2,698,241, 2,
764,520, 2,864,755, 3,4
62,335, 3,475,193, 3,14
No. 3,421, No. 3,501,301, No. 3,46
0,944, 3,674,531, British Patent No. 7
88, 365, 804, 005, 891, 46
No. 9, Japanese Patent Publication No. 48-43122, No. 51-446, etc.).

All of these surface treatments are thought to be caused by the formation of polar groups on the surface of the support, which was originally hydrophobic, and by increasing the crosslink density of the surface. It is considered that the affinity of the component contained in the undercoat liquid with the polar group is increased, or the fastness of the adhesive surface is increased. Also, various arrangements have been made for the composition of the undercoat layer, and a layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and the second layer is photographed as the second layer. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) that adheres well to a layer, and a single layer of applying a single resin layer containing both a hydrophobic group and a hydrophilic group There is a law. Among the surface treatments of (1), corona discharge treatment is the most well-known method, and any conventionally known method, for example, JP-B-48-5.
043, 47-51905, JP-A-47-280.
No. 67, No. 49-83767, No. 51-41770.
No. 51-131576 and the like. Discharge frequency is 50Hz-5000
A suitable frequency is kHz, preferably 5 kHz to several hundreds of kHz.
If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, 0.001 KV · A · min / m ^{2 to 5} KV · A is required to improve the wettability of ordinary plastic films such as polyester and polyolefin.
・ Min / m ² , preferably 0.01 KV ・ A ・ Min / m ^{2 to 1} KV ・
A · min / m ² is appropriate. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.
0 to 2.0 mm is suitable.

In many cases, the glow discharge treatment, which is the most effective surface treatment, is performed by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-2440, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638 and 3,309. No. 299, No. 3,424,735, No. 3,462,335, No. 3,475,307, No. 3,761,299, British Patent 997,093, JP-A No. 53-129262, etc. Can be used. The glow discharge treatment condition is generally a pressure of 0.005 to 20 To
rr, preferably 0.02 to 2 Torr is suitable. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may damage the object to be treated. The electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage can take various values depending on the composition of the atmospheric gas and the pressure, but it is usually 500 within the above pressure range.
A stable steady-state glow discharge occurs between ~ 5000V. A particularly suitable voltage range for improving adhesion is 2000
~ 4000V. Further, as seen in the prior art, a suitable discharge frequency is from DC to several 1000 MHz, preferably 50 Hz to 20 MHz. Regarding the discharge treatment strength, 0.01KV ・
A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.15 KV
・ A ・ min / m ² 〜 1KV ・ A ・ min / m ² is appropriate.

Next, regarding the undercoating method (2), all of these methods have been well researched, and for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used for the first layer of the undercoating in the multilayer method. A large number of polymers such as polyethyleneimine, epoxy resin, grafted gelatin, and nitrocellulose, including copolymers starting from monomers selected from the group consisting of itaconic acid, maleic anhydride, etc. Layers have been investigated for their properties primarily with respect to gelatin. In the single layer method, in many cases, good adhesion is achieved by swelling the support and interfacial mixing with the hydrophilic undercoat polymer. As the hydrophilic undercoat polymer used in the present invention, a water-soluble polymer, a cellulose ester,
Examples include latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch,
Examples thereof include polyvinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer, and examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable. As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol,
Examples thereof include m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred.

Various gelatin hardeners can be used in the subbing layer of the present invention. As a gelatin hardening agent, 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 is S
Inorganic particles such as iO ₂ , TiO ₂ and matting agent or polymethylmethacrylate copolymer particles (1 to 10 μm)
m) can be included. In addition to this, the undercoat liquid may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is generally well-known coating method such as tip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by the extrusion coating method using the hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by the method described in “Coating Engineering”, page 253 (1973, published by Asakura Shoten). Further, the back layer of the support which can be used in the present invention will be described.

The binder for the back layer may be either a hydrophobic polymer or a hydrophilic polymer used in the subbing layer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, a matting agent, a surfactant, a dye and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and for example, as the anionic polymer electrolyte, carboxylic acid and carboxylic acid salt,
A polymer containing a sulfonate is disclosed in, for example, JP-A-48-220.
17, JP-B-46-24159, JP-A-51-30
725, JP-A-51-129216, JP-A-55-
It is a polymer as described in No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
3, JP-A-48-91165, JP-B-49-245.
No. 82 is available. Further, the ionic surfactant has anionic property and cationic property, and is disclosed in, for example, JP-A-49-85826 and JP-A-49-33630.
No., US2,992,108, US3,206,31
2, JP-A-48-87826, JP-B-49-1156
7, JP-B-49-11568, JP-A-55-708.
Compounds such as those described in No. 37 can be mentioned. The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , SnO ₂ , Al ₂ O.
₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃
It is fine particles of at least one crystalline metal oxide or a composite oxide thereof selected from the above. The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The particle size is 0.0
It is desirable that the thickness be 1 to 0.7 μ, particularly 0.02 to 0.5 μ.

Regarding the method for producing the fine particles of the conductive crystalline metal oxide or the composite oxide used in the present invention, JP-A-56-143430 and JP-A-60-258541.
In the specification of the issue. First, a method of producing metal oxide fine particles by firing and performing heat treatment in the presence of a heteroatom that improves conductivity, and second, for improving conductivity when producing kinzoki oxide fine particles by firing. And a method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere during the production of metal fine particles by firing. Examples of containing different kinds of atoms include Al and In for ZnO, Nb and Ta for TiO ₂ , and Sb, Nb and halogen for SnO ₂ . Addition amount of heteroatom is 0.01
The range of .about.30 mol% is preferable, and the range of 0.1 to 10 mol% is particularly preferable.

Next, the silver halide emulsion containing tabular grains used in the present invention will be described. In the present invention, an emulsion composed of tabular grains means that tabular silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 3 or more account for 50% (area) of all silver halide grains in the emulsion. ) It means an emulsion that exists above. An emulsion in which tabular silver halide grains having an aspect ratio of 3 to 15, and more preferably 3 to 10 are present in an amount of 50% (area) or more of all silver halide grains in the emulsion is preferable. The emulsion is present in an amount of 70% or more, particularly preferably 85% or more. Here, the tabular grain is a general term for grains having one twin plane or two or more twin planes. What is a twin plane?
In this case, when the ions at all lattice points on both sides of the (111) plane are in a mirror image relationship, it means the (111) plane. When viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded shape in which these are round, a triangular shape is a triangular shape, and a hexagonal shape is a hexagonal shape. The circular ones have circular outer surfaces parallel to each other. The aspect ratio of the tabular grains in the present invention is a value obtained by dividing the grain diameter of each tabular grain having a grain diameter of 0.1 μm or more by the thickness. The thickness of the particles can be calculated by evaporating the metal from the oblique direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating the shadow length of the latex with reference. I can.

The grain diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the grain. The projected area of the particles is obtained by measuring the area on an electron micrograph and correcting the photographing magnification. The diameter of the tabular grains is preferably 0.15 to 5.0 μm. The thickness of the tabular grains is 0.05 to
It is preferably 1.0 μm. More preferable results may be obtained by using monodisperse tabular grains. A method for producing monodisperse tabular grains is described in, for example, JP-A-63-15161.
No. 8. In the present invention, the tabular silver halide grains contained in the silver halide emulsion preferably have at least an inner core and an outermost shell. In tabular grains, it is possible to laterally displace from the centers of two (111) main planes facing each other to form an inner core and an outermost shell. The region forming the nucleus and the periphery of the main plane is called the outermost shell. Therefore, in this case, both the inner core and the outermost shell can form a surface. Further, in these tabular grains, two (11
1) It is also possible to displace in the direction perpendicular to the main plane to form the inner core and the outermost shell. In this case, the most central region of the sandwich is called the inner core. Further, the inner shell and the outermost shell are displaced laterally from the centers of the two (111) principal planes facing each other, and at the same time, they are vertically displaced to form the sandwich-shaped inner core and the outermost shell. It is also possible that the outer shell is a continuous phase and covers the inner phase, and each of these phases is also called the inner core or outermost shell. The internal nucleus in the tabular halide grains is composed of silver iodobromide, silver chloroiodobromide, silver chloroiodide or silver bromide. Preferably, the inner core is composed of silver iodobromide containing 0 mol% to 12 mol% of silver iodide. More preferably, silver bromide or 6
It consists of silver iodobromide containing less than mol% of silver iodide. The outermost shell of the tabular halide grains is composed of silver chloroiodobromide or silver iodobromide having a higher silver iodide content than the inner core. The silver iodide content of the outermost shell is preferably 1 mol% or more and 40 mol% or less. It is more preferably 2 mol% or more and 30 mol% or less. Most preferably, the tabular silver halide grain in the present invention has at least one intermediate nucleus between the inner nucleus and the outermost shell. This intermediate shell is usually continuous, but it is one or more phases of silver halide which may have a sea-island structure in some cases. The intermediate shell is preferably composed of silver chloroiodobromide, silver iodobromide or silver bromide. These middle shells are
It is preferable to have a halogen-converted halosilver chloride layer, a silver thiocyanate layer or a silver citrate layer described in JP-A-1-102547. When there is one or more intermediate shells,
The silver iodide content of each of these shells is preferably 0 mol% or more and 40 mol% or less. It is more preferably 30 mol% or less, still more preferably 20 mol% or less.

In the present invention, when the silver iodide content of the nucleus and shell of the above-mentioned silver halide grains varies continuously between shells having different silver iodide content or between the core and the shell. Does not exclude taking the average value. The ratio of the inner core, the intermediate core, and the outermost shell to the entire particles is arbitrary. Particularly preferably, the outermost shell has a mole fraction of 5% or more and 50% or less, and more preferably 10% or more and 30% or less. The inner core and the middle shell have a molar ratio of 1: 0.1 to the outermost shell.
It can occupy any ratio from 10 to 10. The silver iodide content of the whole grain can be adjusted by the ratio of the inner core, the middle shell and the outermost shell and the content of each silver iodide, but the preferable silver iodide content of the whole grain is 10 mol% or less, It is preferably 5 mol% or less, particularly preferably 3 mol% or less. In the present invention, it is preferable that the average silver iodide content of each grain of the emulsion is more uniform. The uniformity of the average silver iodide content of the grains can be examined by, for example, the Electron-Probe Micro Analyzer method. The silver halide emulsion consisting of tabular grains used in the present invention is, for example, Cugnac, Chateau.
And Duffin's “Photographic Emulsion Chemistr
y "(Focal Press, New York 1966), p. 66-
Page 72, and “Phot Jou” edited by APH Trilli, WF Smith.
rnal "80 (1940), page 285, JP-A-58-113927 and JP-A-58-11392.
It can be easily prepared by referring to the method described in No. 8 and No. 58-127921. That is, a seed crystal having 40% or more by weight of tabular grains is formed in an atmosphere having a relatively high pAg value of pBr of 1.3 or less, and the same p
Tabular halogenated grains can be obtained by growing seed crystals while simultaneously adding silver and a halogen solution while maintaining the Br value. In this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. Here, the size of the tabular silver halide grain can be adjusted, for example, by controlling the temperature, selecting the type and quality of the solvent, and controlling the addition rate of the silver salt used during grain growth and the halide. . In the present invention, when the tabular silver halide grains are produced, a silver halide solvent is optionally used to control the grain size, the grain shape (aspect ratio, etc.), the grain size distribution, and the grain growth rate. be able to. The amount of the solvent used is 10 ^{−3 to} 1.0 of the reaction solution.
The range of wt% is preferable, and the range of 10 ^-2 to 10 ^-1 wt% is particularly preferable. In the present invention, the particle size distribution can be made monodisperse and the growth rate can be increased with an increase in the amount of solvent used, while the particle thickness tends to increase with the amount of solvent used.

In the production of tabular silver halide grains used in the present invention, the addition rate and the addition rate of a silver salt solution (for example, AgNO ₃ aqueous solution) and a halide solution (for example, KBr aqueous solution) which are added to accelerate grain growth. A method of increasing the amount and the addition concentration is preferably used. Regarding these methods, for example, US Pat. No. 1,335,925,
U.S. Pat. Nos. 3,650,757 and 3,672,9
No. 00, No. 4,242,445, JP-A-55-14.
The description of No. 2329 and No. 55-158124 can be referred to. The tabular grains of the present invention are characterized by containing 20% or more (w / w in terms of silver amount) based on the total silver halide in the light-sensitive material. At least one of the light-sensitive layers constituting the silver halide photographic light-sensitive material, and particularly in the case of a color light-sensitive material, each of the yellow layer, the magenta layer and the cyan layer may be one layer, but preferably each layer is a tabular grain. Is included. In that case, all of the photosensitive silver halide grains are preferably tabular, but as described above, they may be 50% (area) or more of the total silver halide grains in the emulsion, more preferably 70% or more, and particularly preferably 85%. That is all.

The photographic layer of the photographic light-sensitive material will be described.
The silver halide emulsion layer may be any of black and white colors. Here, a 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. The number of layers and the non-photosensitive layer and the order of the layers are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color sensitive layer and the blue color sensitive layer are installed in this order. 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 has a layer of JP-A-61-43748.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470.
No. or British Patent No. 923,045, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
06541, 62-206543, 56-25
No. 738, No. 62-63936, No. 59-20246.
No. 4, Japanese Patent Publication No. 55-34932, No. 49-15495
No. specification. Silver halide grains that can be used in addition to the tabular silver halide of the present invention have regular crystals such as spheres, cubes, octahedra and tetradecahedrons, or irregular crystal forms. , Those having crystal defects such as twin planes, or a composite form thereof.

The grain size of these silver halides is about 0.2.
Fine particles of not more than micron or large size particles having a projected area diameter of up to about 10 microns may be used, and they may be polydisperse emulsions or monodisperse emulsions and are not particularly limited. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (December 1978).
Mon), pp. 22-23, "I. Emulsion prepar
ation and types) ", and the same No. 18716 (197)
Nov. 9), p. 648, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafkides, Chemie e.
t Phisique Photographique, Paul Montel, 196
7), "Photo Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin Photographic Emulsion Chemistry
(Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikm).
an et al., Making and Coating Photographic Emulsio
n, Focal Press, 1964) and the like. U.S. Pat. No. 3,574,6
28, 3,655,394 and British Patent No. 1,
Monodisperse emulsions described in, for example, No. 413,748 are also preferable. 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, or may be joined 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. Additives used in such processes are Research Disclosure N
No. 17643 and No. 18716, the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

(Types of Additives) (RD17643) (RD18716) 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to page 648, right column ~ Page 649 Right column 4 Whitening agent Page 24 5 Antifoggants and stabilizers 24 to 25 pages 649 Right column to 6 Light absorbers, filter dyes, UV absorbers 25 to 26 pages 649 Right column to 650 left columns 7 Anti-staining agent Page 25 Right column Page 650 Left-right column 8 Dye image stabilizer Page 25 9 Hardener 26 Page 651 Left column 10 Binder 26 Same as above 11 Plasticizers and lubricants Page 27 650 Right column 12 Coating Auxiliary agents, surface active agents, pages 26 to 27, page 650, right column Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, they are described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. . Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. issue,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
Those described in 511, 649, European Patent No. 249,473A, etc. are preferable. 5 for magenta coupler
-Pyrazolone-based and pyrazoloazole-based compounds are preferable, and U.S. Pat. Nos. 4,310,619 and 4,35.
1,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984).
June 60), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-72238, and JP-A-6-72238.
0-35730, 55-118034, 60-
185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in WO (PCT) 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 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
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,753,871, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Research Disclosure No. 1 is a colored coupler for correcting unwanted absorption of color forming dyes.
7643, Section VII-G, U.S. Pat. No. 4,163,670.
No. 57/39413, U.S. Pat. No. 4,000
Those described in 4,929, 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 2,125,57.
No. 0, European Patent No. 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, 4,080,211, 4,367,282, and 4,409,320.
U.S. Pat. No. 4,576,910, British Patent 2,102,13.
No. 7, etc.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
Patents described in D17643, VII to F, JP-A-5
7-151944, 57-154234, 60
Those described in U.S. Pat. No. 4,184,248, No. 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. 6, JP-A-62-24252 and the like, DIR redox compound releasing coupler, 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, No. 24241, couplers releasing bleaching accelerators described in JP-A No. 61-201247, couplers releasing ligands described in US Pat. No. 4,553,477, JP-A-63-75747. Examples thereof include couplers that release the leuco dye described.
The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in 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. , Hydrocarbons and the like. 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 T ¹ /
₂ is preferably 30 seconds or less. The film thickness is 25 ° C and relative humidity is 5
Means a film thickness measured at 5% tone humidity (2 days), the film swelling rate T _^1/2 can be measured in accordance with a known method in the art. For example, A Green (A. Gree
n) Photographic Science and
Engineering (Photogr. Sci. Eng.), Volume 19, 2
No., can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _^1/2 is 30 ° C. in a color developing solution, the maximum swollen film to reach when treated for 3 minutes 15 seconds 90% of the thickness and the saturation film thickness and time defined to reach the thickness of the T _^1/2. Film swelling rate T _^1/2 can be adjusted to gelatin as a binder by adding a hardening agent, or by changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, and N.
O. 18716, 615, can be developed by the usual method described in the left column to the right column. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and 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 Disclosures 14,850 and 15,
Schiff base type compound described in No. 159, No. 13,924
No.

[0043]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 1) Preparation of Supports The following Supports A to C were prepared by the method described below. Support A (polyethylene naphthalate (PEN): thickness 40 μm, 80 μm, 122 μm) Support B (polyethylene terephthalate (PET): thickness 90 μm) Support C (triacetyl cellulose (TAC): thickness 1
22 μm) Support A: 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
After drying 2 parts by weight of P.326 (manufactured by Geigy) by a conventional method, it was melted at 300 ° C. and extruded from a T-die 14
Longitudinal stretching of 3.3 times is performed at 0 ° C., and then at 130 ° C. for 3.
After transverse stretching of 3 times and heat setting at 250 ° C. for 6 seconds,
Films with thicknesses of 40, 80 and 122 μm were obtained. Support B: A commercially available polyethylene terephthalate polymer was biaxially stretched and heat-set according to a conventional method to obtain a film having a thickness of 90 μm. Support C: methylene chloride / methanol = 82/8 wt of triacetyl cellulose by a normal solution casting method
Ratio, TAC concentration 13% Plasticizer TPP / BDP = 2 /
1 (where TPP; triphenyl phosphate, BD
T: Biphenyl diphenyl phosphate) 15 wt
% Band method.

2) Coating of Undercoat Layer Each of the supports A and B was subjected to corona discharge treatment on both sides thereof and then provided with an undercoat layer having the following composition. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. At this time, the object to be processed is 0.3
Treatment of 75 KV · A · min / m ² was performed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. Gelatin 3 g Distilled water 25 cc Methanol 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Parachlorophenol 0.3 g Formaldehyde 0.02 g Trimethylolpropane triazine 0.03 g Further, for support C, the following composition is used. A subbing layer was provided. Gelatin 0.2g Salicylic acid 0.1g Methanol 15cc Acetone 85cc Formaldehyde 0.01g

3) Coating of back layer A back layer having the following composition was coated on the surface opposite to the side where the undercoat layer of the supports A to C after undercoating was provided. 3-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were added to 300 parts of ethanol.
It was dissolved in 0 part by weight to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The coprecipitate obtained is left at 50 ° C. for 24 hours,
A reddish brown colloidal precipitate was obtained. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. Do this operation 3
Excess ions were removed repeatedly. 200 parts by weight of the colloidal precipitate from which excess ions were removed was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish tin oxide-antimony oxide composite having an average particle size of 0.2 μm. Fine particle powder of The specific resistance of this fine powder is 2
It was 5 Ω · cm. 40 parts by weight of the fine particle powder and 60 parts of water
Part by weight of the mixed solution was adjusted to pH 7.0 and roughly dispersed with a stirrer, then a horizontal sand mill (trade name Dynomill; WILLYA. BACH
OFENAG) was dispersed and prepared until the residence time reached 30 minutes.

3-2) Preparation of back layer: the following formulation [a]
To a dry film thickness of 0.3 μm
And dried for 30 seconds. Further, the following coating solution (b) for coating layer was applied thereon to give a dry film thickness of 0.1 μm,
It was dried at 130 ° C. for 2 minutes. [Formulation a] The conductive fine particle dispersion liquid 10 parts by weight Gelatin 1 part by weight Water 27 parts by weight Methanol 60 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0.01 parts by weight [Coating layer coating liquid (b)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight

4) Heat Treatment of Support After coating an undercoat layer and a back layer by the above method, Table 1
The heat treatment was performed under the conditions shown in. All the heat treatments were carried out with the core having a diameter of 30 cm and the outer surface of the undercoat surface wound.

[0048]

[Table 1]

As a comparative example, a non-heat-treated product was also prepared. 5) Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the composition shown below was multilayer-coated to prepare multilayer color photosensitive materials 1-1 to 1-19. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Emulsion silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS -2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion Silver 0.5 Exhibited in Table 2 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC -3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion Silver 0.70 Table 2 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC -2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC -3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low-Sensitivity Green Sensitive Emulsion Layer) Emulsion Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM -0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion Silver 0.80 Described in Table 2 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM -3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

9th layer (high-sensitivity green emulsion layer) Emulsion silver 1.25 Exhibited in Table 2 ExS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 3.2 × 10 ⁻⁴ ExC-1 0.010 ExM -1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

11th Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

12th layer (medium-speed blue emulsion layer) Emulsion silver 0.40 ExS-7 7.4 × 10 ⁻⁴ ExC-7 7.0 × 10 ⁻³ ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion Silver 1.00 Exhibited in Table 2 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Emulsion silver 0.20 described in Table 2 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

[0065]

[Table 2]

Further, W-1 to W-3, B-4 to B- are added to each layer in order to improve storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0067]

[Table 3]

In Table 3, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0069]

[Chemical 6]

[0070]

[Chemical 7]

[0071]

[Chemical 8]

[0072]

[Chemical 9]

[0073]

[Chemical 10]

[0074]

[Chemical 11]

[0075]

[Chemical 12]

[0076]

[Chemical 13]

[0077]

[Chemical 14]

[0078]

[Chemical 15]

[0079]

[Chemical 16]

[0080]

[Chemical 17]

[0081]

[Chemical 18]

[0082]

[Chemical 19]

[0083]

[Chemical 20]

<Processing> Treatment step Temperature time Color development 38 ° C. 3 minutes Stop 38 ° C. 1 minute Washing with water 38 ° C. 1 minute Bleaching 38 ° C. 2 minutes Washing with water 38 ° C. 1 minute Fixing 38 ° C. with water 2 minutes 38 ° C. 1 minute Stabilizing bath 38 ° C. 1 minute The treatment liquid used has the following composition. Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide 0.4g Sodium chloride 1g Hoh sand 4g Hydroxylamine sulfate 2g Ethylenediaminetetraacetic acid disodium dihydrate 2g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline monosulfate) 4g Water is added and the total amount is 1 liter Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70% aqueous solution) 30 ml Acetic acid 30 ml Sodium acetate 5 g Potassium alum 15 g Total amount 1 liter Bleach Liquid Ethylenediaminetetrairon (III) acetate sodium dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Folic acid 5 g Ammonia water Adjusting pH to 5.0 Total volume with water 1 liter Fixing solution Sodium thiosulfate 150 g Sodium sulfite -Soda 15g Ho sand 12g Glacial acetic acid 15ml Potassium alum 20g Water added to a total amount of 1 liter Stabilization bath Folic acid 5g Sodium citrate 5g Sodium metaphorate (tetrahydrate) 3g Potassium alum 15g Water added to a total amount 1 liter

6) Evaluation Results The samples prepared in Table 1 were evaluated as shown in Table 1. Flexural modulus (ring method) A sample having a width of 35 m and a circumference of 10 cm was placed horizontally, and a load was applied to the upper part to measure the load when the amount of deformation was 12 mm. The larger the value, the larger the elastic modulus. The measurement was performed at 25 ° C. and 60% RH. The core set sample film was slit into a width of 35 mm and a length of 1.2 m. After humidity control of this at 25 ° C. and 60% RH overnight, the photosensitive layer was wound inside and wound on a spool of 6 to 14 mm as shown in Table 1. Place this in a sealed container and hold at 80 ° C for 2
It was heated for an hour and wound. This temperature condition is a condition assuming that the film was placed in the car in the summer. Development processing and curl measurement After the film wound under the above conditions was left to cool overnight in a room at 25 ° C, a sample film was taken out from the sealed container, and this was processed by an automatic processor (Minilab FP-550).
B: manufactured by Fuji Photo Film Co., Ltd.) and immediately processed at 25 ° C
The curl was measured using a curl plate under 60% RH. The development processing conditions are as follows.

Fogging over time The sample was slit into a width of 35 mm and a length of 1.5 m, wrapped around the core set spool shown in Table 1 and fixed at the end with cellophane tape, and then stored in an aluminum-coated sealed bag for a period of time. Some of the conditions used were humidity controlled at 25 ° C. and 60% RH for 3 hours, then put in a sealed bag and heated to 50 ° C. for 28 days. Further, a part of them was conditioned at 30 ° C. and 80% RH for 3 hours, put in a sealed bag and aged at 40 ° C. for 21 days. The fog degree of the sample not subjected to these treatments is set to 100%,
The fog value over time is shown in%. <Cartridge storability> When the outer diameter of the cartridge is set to 21 mm, if the core diameter of the spool is too large, the photosensitive material cannot be sufficiently stored, and the cartridge storability is poor. The evaluation shows whether 36 135 size formats can be stored in a cartridge having an outer diameter of 21 mm. ○
Indicates that it can be stored, and × indicates that it cannot be stored.

As can be seen from Table 1, Comparative Samples 1-1 and 1-2 using the conventional TAC have a bad development process trouble.
Further, the fog with time and the cartridge storability were poor. In Comparative Samples 1-3 to 1-4, since the support was PET and the Tg was low, the development processing trouble was extremely bad. At that time, the development processing trouble was not improved even in the case of Sample 1-4 which was previously heat-treated. Furthermore, Sample 1-5, which used the polyester of the present invention but was not heat-treated, caused processing trouble. On the other hand, the polyester (PEN) of the present invention was used and the tabular grains were
Inventive samples 1-7 to 1-9, 1-1 used at 0% or more
Nos. 1, 1-12, 1-14, and 1-17 also had a large curl reduction rate, and had little trouble in development processing and fogging. Also, as shown in Comparative Sample 1-10, the core is 1
Since it was 2 mm, it was very inferior in cartridge storage. Also, the comparative sample 1 whose core diameter is too small as 3.5 m
-18 had a winding tendency and had troubles in the minilab. In addition, Sample 1 using no tabular grains of the present invention
Sample 1-13 having 6 and 20% or less of tabular grains had poor fog with time. Furthermore, comparative sample 1-
Nos. 15 and 1-16 are polyesters other than the present invention having a Tg of 205 ° C. (Comparison a), poly (oxyterephthaloyloxy-1,4-phenylene isopropylidene-1,4-phenylene) The sample changed to No. 1) caused development processing troubles even after heat treatment and had a large fog with time. Furthermore, Comparative Sample 1-19, which uses tabular grains having an aspect ratio larger than that of the present invention, has poor fog with time. From the above, it can be seen that the sample of the present invention satisfies the performance in all respects, and the present invention is excellent.

[0088]

EFFECT OF THE INVENTION Core diameter of spool in cartridge 1
In a silver halide photographic light-sensitive material accommodated in 0 mm or less, the support of the light-sensitive material is polyester having a glass transition temperature of 90 ° C. or higher, and at least one silver halide emulsion contains tabular grains in all emulsions. By containing 20% by weight or more, it was possible to obtain a light-sensitive material having excellent flexural modulus and curl value (curl reduction rate), and having no trouble in development processing and fog over time.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material in which a silver halide photographic light-sensitive material is contained in a spool having a core diameter of 10 mm to 4 mm in a cartridge, and a glass transition temperature of a support of the light-sensitive material is 90 ° C. or more and 200 ° C. A silver halide photographic light-sensitive material comprising the following polyester, wherein at least one silver halide emulsion contains tabular grains in an amount of 20% by weight or more of the total emulsion. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the tabular emulsion is a tabular silver halide grain having an aspect ratio (equivalent circle diameter of silver halide grain / grain thickness) of 3 to 15. 3. A silver halide photographic light-sensitive material according to claim 1, wherein the tabular silver halide grains having an aspect ratio of 3 or more are emulsions in which 50% (area) or more of all silver halide grains in the emulsion are present. . 4. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is wound into a cartridge having a spool having a core diameter of 8 mm or less. 5. The halogen according to claim 3, wherein the polyethylene naphthalate and its derivative have a glass transition point of 90 ° C. or higher and are heat-treated at a glass transition point of −5 ° C. or lower. Silver halide photographic light-sensitive material.