JPH07219146A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material having an excellent dynamic characteristic even if it is made thin, having a substrate which is hardly curled and further excellent in adhesion resistance. CONSTITUTION:This silver halide photographic sensitive material has a silver halide emulsion layer on at least one side of a substrate. The polyester substrate has 50 to 200 deg.C glass transition temp. (Tg), the substrate is heat-treated at (Tg-50 deg.C) to Tg for 0.1 to 1500hr, and the thickness is controlled to be 50 to 300mum. At least one layer on the side having the silver halide emulsion layer contains adeveloper-soluble matting agent having 1 to 10mum number average grain diameter with the number of grains having + or -60% of the number average grain diameter controlled to >=80% and a developer-insoluble matting agent respectively at 1 to 1000mg/m<2>.

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, and in particular, by containing fine particles having a narrow grain size distribution in at least one layer on the side having a silver halide emulsion layer, excellent blocking properties and mechanical properties are obtained. The present invention relates to a silver halide photographic light-sensitive material having a glass derivative having a glass transition temperature (Tg) of 50 to 300 ° C. and a thickness of 50 to 300 μm, which is excellent in curling tendency and is hard to be rolled, on a support.

[0002]

Photographic light-sensitive materials are generally prepared by coating at least one photographic light-sensitive layer on a plastic film support. This plastic film is generally triacetyl cellulose (hereinafter referred to as "T
Fiber-based polymers represented by "AC") and polyester-based polymers represented by polyethylene terephthalate (hereinafter referred to as "PET") are used. As the photographic light-sensitive material, a roll film such as a color or black-and-white negative, which is stored in a cartridge with a width of 35 m / m or less and is loaded into a camera and used for photographing,
There are X-ray films, plate-making films, and sheet films such as cut films.

By the way, in recent years, the downsizing of photographing apparatuses has been remarkably advanced from the viewpoint of handleability. With the downsizing of the photographing device, there is an increasing demand for downsizing the cartridge. Conventionally, in the 135 system, a cartridge having a diameter of 25 mm has been used. However, if the diameter of the spool (winding core) is reduced, and at the same time, the thickness of the support used in the existing 135 system is reduced, the cartridge is further improved. It can be miniaturized. However, there are three problems to be solved in order to reduce the size of the cartridge by the above method. The first problem is a decrease in mechanical strength as the support becomes thinner.

The second problem is a strong curl during storage over time which accompanies the miniaturization of cartridges.

A third problem is that the film winding strength is increased by reducing the diameter of the spool, and the adhesive failure between the emulsion surface and the back surface is likely to occur during storage in a cartridge, especially under high temperature and high humidity. . However, in order to obtain sufficient blocking properties by itself, the conventional matting agents need to be present in a considerably large amount in the surface layer, and the photographic properties of the photographic light-sensitive material after development processing (transparency and granularity) It had a drawback that it markedly deteriorated the property).

As a method for obtaining a photographic light-sensitive material satisfying both blocking property and photographic property, for example, JP-A-59-59
149357 and JP-A-61-230141 describe the use of polymer particles having a narrow particle size distribution.
With a light-sensitive material in which the film winding strength is increased by winding the film on a spool having a small diameter, it was not possible to obtain a photographic light-sensitive material having both blocking property in a cartridge and photographic property after development processing. Therefore, there is a need for a new technique for improving the blocking property, which has both the blocking property in the film cartridge with the increased film winding strength and the photographic property after the development processing.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photographic light-sensitive material which has excellent mechanical properties even when it is thinned, has a support which is hard to have a curling tendency, and is excellent in blocking property. To provide.

[0008]

These problems are solved in a silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of a support, wherein the support has a glass transition temperature (Tg) of 50 ° C to 50 ° C. At 200 ° C, Tg ~ (Tg-5
It is a polyester support characterized in that it is heat-treated at 0 ° C.) for 0.1 to 1500 hours and has a thickness of 50 to 300 μm, and at least one layer on the side having a silver halide emulsion layer has a number average grain size. The developing treatment solution-soluble matting agent and the development treatment solution-insoluble matting agent having the number of particles present in the particle size range of 1 to 10 μm and ± 60% of the number average particle diameter of 80% or more are 0 respectively. 1-1000
It was achieved in a silver halide photographic light-sensitive material characterized by containing mg / m ² . First, the matting agent of the present invention used for improving the blocking property will be described.
The matting agent of the present invention has a number average particle diameter of 1 μm to 10 μm.
And a developing treatment solution-soluble matting agent and a developing treatment solution-insoluble matting agent in which the number of particles present in the particle diameter range of ± 60% of the number average particle diameter is 80% or more. The number average particle diameter of these matting agents is preferably 1.5 μm to 8 μm.
It is more preferably 1.5 μm to 6 μm, and further preferably 2 μm to 6 μm. In addition, the particle size distribution is preferably such that the number of particles present in a particle size range of ± 50% of the number average particle size is 90% or more, and more preferably within a particle size range of ± 40% of the number average particle size. The number of particles present is 90% or more, more preferably the number of particles present in the particle size range of ± 30% of the number average particle size is 90% or more, particularly preferably the particle of ± 20% of the number average particle size. The number of particles existing in the diameter range is 90% or more. The number average particle size and particle size distribution in the present invention can be examined by taking an electron micrograph of the matting agent and randomly measuring the particle size of 500 or more matting agents from the photograph.

The matting agent content is 0.1 each.
To 1000 mg / m ² , preferably 1 to 500 mg / m ^2.
m ^2, more preferably 5 to 300 mg / m ^2, more preferably from 10 to 200 mg / m ^2. If the number average particle size is smaller than 1 μm, the transparency of the photosensitive material after development is remarkably deteriorated, and if it is larger than 10 μm, the graininess is deteriorated. Further, if the content of the matting agent is 0.1 mg / m ² or less, the blocking property is deteriorated, and if it is 1000 mg / m ² or more, the transparency of the photosensitive material after development processing is deteriorated. Further, in the present invention, as the matting agent, a matting agent soluble in the developing treatment solution and a matting agent insoluble in the developing treatment solution are contained together. By reducing the diameter of the spool, the winding strength of the film becomes stronger, and the emulsion surface and the back surface are likely to suffer adhesion failure during storage in a cartridge, especially under high temperature and high humidity. Therefore, when it is wound on a spool and stored in a cartridge, it is preferable that the content of the matting agent is large in order to improve the blocking property. On the other hand, if a large amount of the matting agent is contained in the photosensitive material after the development processing, it becomes a factor that deteriorates transparency and graininess. Therefore, it is preferable that the content of the matting agent is small after the development processing. To solve this problem, the cartridge contains a matting agent that is soluble in the developing solution and a matting agent that is insoluble in the developing solution to improve the blocking property. It is preferred that the soluble matting agent, which retains the above blocking property, is dissolved in the processing liquid to eliminate it from the light-sensitive material to improve transparency and graininess. Insoluble matting agent /
The ratio of the soluble matting agent is not particularly limited, but is 10/1 to
1/10 is preferable, and more preferably 5/1 to 1/10
And more preferably 4/1 to 1/6.

The layer containing the matting agent of the present invention is not particularly limited, and it can be contained in any layer on the emulsion side or the back side, and may be contained in a plurality of layers. The emulsion side is particularly preferable, and the outermost layer on the emulsion side is most preferable.
The thickness of the layer containing the matting agent of the present invention is not particularly limited, but is preferably 0.05 to 10 μm, more preferably 0.15 to 6 μm, and further preferably 0.15 to 5 μm.
It is 3 μm. Further, the average height of the surface protrusions formed by the matting agent is 0.02 to 8 μm, preferably 0.1.
It is 1 to 8 μm, more preferably 0.1 to 6 μm, and particularly preferably 0.5 to 5 μm. The matting agent used is not particularly limited, but an inorganic compound or a polymer compound having a glass transition temperature (Tg) of 40 ° C. or higher is preferable. Among them, the preferred T of the matting agent of the polymer compound
g is 50 ° C. or higher, more preferably 60 ° C. or higher. If the Tg is less than 40 ° C., the blocking property becomes worse in an environment where the temperature is 40 ° C. or higher, which is not preferable.

The refractive index of the matting agent of the present invention is preferably within ± 0.5 with respect to the refractive index of the binder of the layer containing the matting agent. The refractive index of the matting agent of the present invention is
It is better that the refractive index of the binder of the layer containing the matting agent is as close as possible, preferably ± 0.
4 or less, more preferably ± 0.3 or less, further preferably ± 0.2 or less, and particularly preferably ± 0.1 or less. If the refractive index of the matting agent of the present invention is out of the range of ± 0.5 with respect to the refractive index of the binder of the layer containing the matting agent, it becomes a factor that extremely deteriorates transparency and graininess, which is not preferable. Two or more kinds of the matting agent of the present invention can be mixed and used. The matting agent of the inorganic compound of the present invention, for example,
There are fine powders of barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, silicon dioxide, etc. Titanium dioxide (rutile type or anatase type) and the like. In addition, the particle size is relatively large,
For example, it can also be obtained by crushing from an inorganic substance of 20 μm or more and then classifying (vibrating filtration, air classification, etc.).
As the matting agent of a polymer compound, there are polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch and the like, and pulverized and classified products thereof.

Alternatively, a polymer compound synthesized by a soap-free polymerization method or a suspension polymerization method, a polymer compound spherically formed by a spray drying method or a dispersion method, or an inorganic compound can be used. Further, as a specific method for obtaining the polymer compound matting agent of the present invention, there is disclosed in JP-A-61-61
Techniques such as those described in 230141 are also preferred.
For example, in an aqueous dispersion of seed particles of uniform particle size made by soap-free polymerization, the solubility in water is 0.02% by weight.
Hereinafter, a swelling aid having a molecular weight of 5000 or less is added to absorb the swelling aid to increase the monomer absorption capacity of the fine particles, and then the monomer is added to the seed particles in a volume conversion of 100 to 1
It is described that the product is polymerized after being enlarged by about 0000 times or more.

The polymer compound matting agent of the present invention is made from one or more monomer compounds as described below. Specific examples of the monomer compound, acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, phthalic acid diesters, and the like, as ester residues, methyl, ethyl, propyl, Isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl, phenyl, 2-hydroxyethyl, 2-ethoxyethyl, glycidyl, ω-methoxy polyethylene glycol. (Additional mol number 9) and the like. In addition, vinyl esters, olefins, styrenes, acrylamides,
Methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, unsaturated nitriles and the like are also preferably used.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (for example,
Monoethyl itaconate, etc .; monoalkyl maleate (eg, monomethyl maleate, etc .; styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (eg,
Acryloyloxymethyl sulfonic acid etc.); methacryloyloxyalkyl sulfonic acid (eg methacryloyloxyethyl sulfonic acid etc.); acrylamidoalkyl sulfonic acid (eg 2-acrylamido-2-
Methyl ethane sulfonic acid etc.); Methacrylamide amidoalkyl sulfonic acid (eg 2-methacrylamido-2-
Methyl ethane sulfonic acid, etc.); acryloyloxyalkyl phosphate (eg, acryloyloxyethyl phosphate, etc.); These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Still other monomer compounds include U.S. Pat. Nos. 3,459,790, 3,438,708, 3,554,987,
No. 4,215,195, No. 4,247,673
And the crosslinkable monomers described in JP-A No. 57-205735 and the like can be used. Specific examples of such a crosslinkable monomer include N- (2
-Acetoacetoxyethyl) acrylamide, N- (2
Examples include-(2-acetoacetoxyethoxy) ethyl) acrylamide and the like. Among these monomer compounds, acrylic acid and its esters, methacrylic acid and its esters, vinyl esters, styrenes and olefins are preferably used, and among them, acrylic acid and its esters are particularly preferred. , Methacrylic acid and its esters, and styrene. Also,
The present invention includes JP-A Nos. 62-14647 and 62-177.
Particles having a fluorine atom or a silicon atom as described in No. 44 and No. 62-17743 may be used. Among the matting agents of the present invention, acrylic acid, its esters, methacrylic acid, its esters, and styrene are particularly preferable as the matting agent in a total composition of 8 parts.
The matting agent is contained in an amount of 0 wt% or more, and in particular, it is most preferable to contain a total of 90 wt% or more.

For example, the preferred polymer compound matting agent of the present invention will be described. Methyl methacrylate / acrylic acid copolymer (97/2 to 40/60 (molar ratio)), methyl methacrylate / methacrylic acid copolymer. Polymers (97/2 to 40/60 (molar ratio)), styrene / acrylic acid copolymers (97/2 to 40/60 (molar ratio)), and among them, more preferred is methyl methacrylate / acrylic acid. Copolymer (95/5 to 45/55 (molar ratio)), methyl methacrylate / methacrylic acid copolymer (95/5 to 45/55 (molar ratio)), styrene / acrylic acid (95/5) To 45/55 (molar ratio)), more preferably a methyl methacrylate / acrylic acid copolymer (93/7 to 50/50 (molar ratio)), a methyl methacrylate / methacrylic acid copolymer. 93 / 7-50 / 50
(Molar ratio)), styrene / acrylic acid (93/7 to 50)
/ 50 (molar ratio)). Regarding the matting agent insoluble in the developing solution, the content of acrylic acid and methacrylic acid combined in the composition of the matting agent is preferably 0 to 35 wt%,
More preferably 3 to 25 wt%, and even more preferably 5 to 2
It is 0 wt%. Further, regarding the developing agent-soluble matting agent, the total content of acrylic acid and methacrylic acid in the composition of the matting agent is preferably 60 to 35 wt%, more preferably 55 to 40 wt%, and further preferably 53 to 43.
wt%.

Acrylic acid preferably used in the present invention,
And its esters, methacrylic acid, its esters, and a polymer compound matting agent containing styrene as a main component have a weight average molecular weight of 5,000 to 500,000, preferably 5,000 to 100,000, and more preferably Is 7,
000 to 70,000, particularly preferably 10,000 to
It is 50,000. Examples of preferred inorganic compounds and polymer compounds of the present invention are silica, polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / acrylic acid = 90/1.
0, or 55/45 (molar ratio)), poly (styrene / acrylic acid = 95/5, or 60/40 (molar ratio)), poly (methyl methacrylate / methacrylic acid = 90/10,
Or 54/46 (molar ratio)), poly (styrene / styrene sulfonic acid = 95/5, or 60/40 (molar ratio)), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50 / 40 /
10 (molar ratio)) and the like. Further, as the particles of the present invention, particles having a reactive (particularly gelatin) group described in JP-A No. 64-77052 and European Patent No. 307855 can be used. Specific examples of the matting agent of the present invention are shown below, but the invention is not limited thereto.

[0017]

[Chemical 1]

[0018]

[Chemical 2]

It is further preferable that fine particles made of an inorganic compound or an organic compound having a number average particle diameter of 1 μm or less are contained in a layer within 5 layers from the layer containing the matting agent of the present invention to the support side. Further, it is particularly preferable that the fine particles are insoluble in the developing solution. The fine particles may be contained in any layer as long as they are within 5 layers on the support side, and may be contained in a plurality of layers. The fine particles are different from the matting agent of the present invention which imparts unevenness to the surface of the light-sensitive material to improve the blocking property, so that the matting agent of the present invention forms a photosensitive layer in a film under high temperature and high humidity conditions. It has the effect of preventing sinking and further improving the blocking property. The particle size distribution of the fine particles is not particularly limited, but preferably, the number of particles present in the particle size range of ± 60% of the number average particle size is 80% or more, more preferably ± 50% of the number average particle size. The number of particles present in the particle size range is 90% or more, and more preferably the number of particles present in the particle size range of ± 40% of the number average particle size is 90%.
% Or more, and particularly preferably ± 30 of the number average particle size
The number of particles existing in the range of the particle diameter is 90% or more. If the fine particles are larger than 1 μm, unevenness on the surface of the photosensitive material is increased, which is a factor that deteriorates transparency and graininess, which is not preferable. Further, if the particle size distribution is widened and the frequency of particles having a large particle size is increased, the unevenness of the surface of the photosensitive material is also increased, which is a factor of deteriorating transparency and graininess, which is not preferable.

The content of the fine particles is 0.
1 to 2000 mg / m ² , preferably 1 to 1500 mg
/ M ² , more preferably 10 to 1000 mg / m ² , and even more preferably 50 to 500 mg / m ² . When it is less than 0.1 mg / m ^{2, the} effect of suppressing the sinking of the matting agent of the present invention is small, and when it is more than 2000 mg / m ² , the film of the layer containing fine particles is embrittled, which is not preferable. The refractive index of the fine particles is ± relative to the refractive index of the binder of the layer containing the fine particles.
It is preferably within 0.5. The refractive index of the fine particles of the present invention should be as close as possible to the refractive index of the binder of the layer containing the fine particles, preferably ± 0.4 or less, more preferably ± 0.3 or less, and even more preferably the refractive index of the binder. Is within ± 0.2, particularly preferably within ± 0.1. If the refractive index of the fine particles of the present invention deviates from the range of ± 0.5 with respect to the refractive index of the binder of the layer containing the fine particles, it becomes a factor that deteriorates transparency and graininess, which is not preferable.
The layer containing the fine particles is preferably close to the layer containing the matting agent of the present invention, and particularly preferably the layer containing the present invention or a layer immediately below it. The closer to the layer containing the matting agent of the present invention, the greater the effect of preventing sinking of the matting agent, which is preferable.

It is preferable that the photosensitive material does not have surface irregularities by containing the fine particles. If unevenness is given, it becomes a factor that deteriorates transparency (haze). The increase in haze due to the inclusion of the fine particles may be 7 or less, preferably 5 or less, more preferably 3 or less, still more preferably 1 or less as compared with the case where no fine particles are contained. The thickness of the layer containing the fine particles is not particularly limited, but is preferably 0.05 to 10 μm, more preferably 0.15 to 6 μm, and further preferably 0.15 to 3 μm. The fine particles may be an inorganic compound or an organic compound, and may have the same composition as the above matting agent of the present invention. Two or more kinds of these fine particles can be mixed and used.
If the binder of the layer containing fine particles is mainly composed of gelatin, silicon dioxide (such as silica) and a polymer compound are preferable. Among them, silica and acrylic acid esters, methacrylic acid esters, vinyl esters,
Polymer compounds obtained from monomer compounds such as styrenes and olefins are particularly preferable. Particles preferably used in the polymer compound include, for example, polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / acrylic acid = 90/10 (molar ratio)), poly (styrene / acryl). Acid = 95/5 (molar ratio)), poly (methyl methacrylate / methacrylic acid = 90/10 (molar ratio)), poly (styrene / styrene sulfonic acid = 95/5 (molar ratio)), polyacrylonitrile, poly (Methyl methacrylate / ethyl acrylate / methacrylic acid = 50/40/10 (molar ratio)) and the like can be mentioned.

The binder of the layer containing the matting agent of the present invention is not particularly limited and may be a lipophilic binder or a hydrophilic binder. The same applies to the binder of the layer containing the above-mentioned fine particles. As the lipophilic binder, known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins and mixtures thereof can be used. The Tg of the resin is −40 ° C. to 200 ° C., and the weight average molecular weight is 10,000 to 300,000, preferably 10,000 to 100,000. Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymers, vinyl chloride, copolymers of vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / vinyl chloride. Acrylonitrile copolymer, vinyl-based copolymer such as ethylene / vinyl acetate copolymer, nitrocellulose, cellulose acetate propionate, cellulose derivative such as cellulose acetate butyrate resin, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, Polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin,
Amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, silicone resin,
Fluorine-based resins and the like can be mentioned.

Of these, vinyl chloride resin poly (meth) acrylic ester resin, cellulose derivative, acrylic resin, urethane resin and styrene resin are preferable. As the radiation curable resin, the above-mentioned thermoplastic resin to which a group having a carbon-carbon unsaturated bond is bonded as a radiation curable functional group is used. Preferred functional groups include an acryloyl group and a methacryloyl group. In the binder molecules listed above, polar groups (epoxy group, CO ₂ M, O
H, NR ₂ , NR ₃ X, SO ₃ M, OSO ₃ M, PO ₃
M ₂ , OPO ₃ M ₂ , where M is hydrogen, alkali metal or ammonium, and when there are plural Ms in one group, they may be different from each other, R is hydrogen or an alkyl group) May be introduced. The polymer binders listed above may be used alone or as a mixture of several types, and a known isocyanate-based crosslinking agent and / or a radiation-curable vinyl-based monomer may be added for curing treatment.

Further, as the hydrophilic binder used,
Research Disclosure No.17643, 26
Page, and No. 18716, page 651, water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. are exemplified.
As the water-soluble polymer, gelatin, gelatin derivatives,
Examples thereof include casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer and the like, and examples of 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. Gelatin is a so-called alkali-processed (lime-processed) gelatin that is immersed in an alkali bath before extraction of gelatin, an acid-processed gelatin that is immersed in an acid bath, and a double-immersed gelatin that has been subjected to both of these processes in the manufacturing process. Any of gelatin may be used. If necessary, a portion of colloidal albumin, casein,
Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide Alternatively, these derivatives, partial hydrolysates, gelatin derivatives and the like may be used in combination with gelatin.

It is preferable to harden the matting agent of the present invention and the hydrophilic binder layer containing the above-mentioned fine particles. Examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, diacetyl and cyclopentanedione. Ketone compounds such as, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-
1,3,5-triazine and others US Pat. No. 3,28
No. 8,775, No. 2,732,303, British Patent No. 9
74,723, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine In addition, compounds having reactive olefins described in U.S. Pat. Nos. 3,635,718, 3,232,763, and British Patent 994,869, N-hydroxymethylphthalimide, and other United States Patent No. 2,732,316,
N-methylol compounds described in US Pat. No. 2,586,168 and the like, isocyanates described in US Pat. No. 3,103,437, US Pat.
7,280, 2,983,611 and the like, aziridine compounds, US Pat. No. 2,725,29
4, acid derivatives described in US Pat. No. 4,725,295, epoxy compounds described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid. be able to. Alternatively, as a hardener for inorganic compounds, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-326.
99, Belgian Patent 825,726, JP-A-60-
225148, JP-A-51-126125, JP-B-58-50699, JP-A-52-54427, U.S. Pat. No. 3,321,313 and the like. it can.

The amount of the hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 2 based on the dry binder.
It is 0% by weight. The matting agent-containing layer described above may contain various additives such as a smoothing agent, a surfactant, an antistatic agent, a thickener, an ultraviolet absorber, a silver halide and a formalin scavenger, if necessary. You can Next, the support used in the present invention will be described. The support used in the present invention has a glass transition temperature (Tg) of 50 ° C to 20 ° C.
It is a polyester derivative (polyethylene aromatic dicarboxylate polyester) at 0 ° C. Tg here
Is defined as follows using a scanning differential thermal analyzer (DSC) in the form of a biaxially stretched film for a light-sensitive material. First, 10 mg of a sample is heated in a nitrogen stream at a heating rate of 20
After heating up to 300 ° C. at a rate of ° C./min, it is rapidly cooled to room temperature.
Then, the arithmetic average value of the temperature at which the temperature starts to deviate from the baseline when the temperature is raised again at 20 ° C./minute and the temperature at which the temperature returns to the new baseline is Tg.

The support comprising a polyester derivative (polyethylene aromatic dicarboxylate polyester) having a Tg of 50 ° C. to 200 ° C. according to the present invention is preferably formed by using a diol and an aromatic dicarboxylic acid as components, but other It is also possible to use a mixture with the above dicarboxylic acid. Dicarboxylic acids that can be used include terephthalic acid, isophthalic acid,
Phthalic acid, phthalic anhydride, naphthalenedicarboxylic acid (2,6-, 1,5-, 1,4-, 2,7-), diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride, succinic acid, Glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4 -Cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1,1-dicarboxy-2-phenylethylene, 1,4-dicarboxymethylphenol,
1,3-dicarboxy-5 phenylphenol, sodium 3-sulfoisophthalate, etc. can be mentioned. Among the above-mentioned dicarboxylic acids, preferred aromatic dicarboxylic acids are those having at least one benzene nucleus. Examples of the diol include ethylene glycol,
1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 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, dimethylolnaphthalene, P-hydroxyethyloxybenzene, bisphenol A, and the like. Also,
If necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester derivative of the present invention includes a hydroxyl group and a carboxyl group (or its ester) in the molecule.
It does not matter even if a compound having at the same time is copolymerized, and examples thereof include salicylic acid. Among these dicarboxylic acid and diol monomers, 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), and paraphenylene are particularly preferable aromatic dicarboxylic acids. Dicarboxylic acid (PPDC), as a particularly preferred diol, is (poly) ethylene glycol (PEG or E).
G)), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A
Examples thereof include (BPA), biphenol (BP), and a copolymerized component of hydroxycarboxylic acid such as parahydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA). Among the above polyester derivatives composed of dicarboxylic acids and diols, more preferred are polyethylene terephthalate (PET), polyethylene-2,6-dinaphthalate (PEN), polyarylate (PAr), polycyclohexanedimethanol terephthalate ( PC
Homopolymers such as T) and dicarboxylic acids of 2,6
-Naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHD)
C), para-phenylenedicarboxylic acid (PPDC), diol as ethylene glycol (EG), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), para as hydroxycarboxylic acid. Examples thereof include copolymers obtained by copolymerizing hydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA).

Specifically, a copolymer of naphthalene dicarboxylic acid, terephthalic acid and ethylene glycol (the mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is preferably 0.3: 0.7 to 1.0: 0, and 0). .5:
0.5-0.8: 0.2 is more preferable. ), 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.0.1: 0.9 is more preferable), isophthalic acid, paraphenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 1 when terephthalic acid is 1). 0.1-10.
0, 0.1 to 20.0, more preferably 0.2 each
It is -5.0 and 0.2-10.0. ), Naphthalenedicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is preferably from 1: 0 to 0.7:
0.3, and more preferably 0.9: 0.1-0.
It is 6: 0.4. ) Terephthalic acid, copolymer of 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-
It is 0.7: 0.3. ), Isophthalic acid, paraphenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0.1-0.5, 0.1-0 when terephthalic acid is 1, respectively). .5, and more preferably 0.2 to 0.3 and 0.2 to 0.3 respectively),
Copolymer of terephthalic acid, neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is preferably 1: 0 to 0.7: 0.3, 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), para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid, ethylene glycol is preferably 1.0:
0 to 0.1: 0.9, more preferably 0.9:
It is 0.1-0.2: 0.8. ) And the like. Among these, particularly preferred are PET and polyethylene 2,6-naphthalate (PEN).

The preferred average molecular weight range of the polyester derivative of the present invention is about 5,000 to 500,000, particularly 5,000 to 200,000. 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, an ester exchange reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, they can be synthesized. Also, the acid component is set as an acid halide,
It may be reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. These polyester synthesis methods are described, for example, in Polymer Experimental Science No. 5
Volume "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980) No. 10
Pages 3 to 136, "Synthetic Polymer V" (Asakura Shoten, 19
71) pp. 187-286 can be referred to.

Further, these polyesters may be partially blended with another polyester or copolymerized with the monomers constituting the other polyester in order to improve the adhesiveness with other polyesters, or A monomer having an unsaturated bond can be copolymerized with these polyesters to be radically crosslinked. Polymer blends obtained by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482, 64-64325, JP-A-3-192718 and Research Disclosure 28.
3,739-41, 284, 779-82, 29.
It can be easily formed according to the method described in 4,807-14. For example, PEN and PET (composition ratio is preferably 0.3: 0.7 to 1.0: 0, more preferably 0.5: 0.5 to 0.8: 0.2), PET.
And PAr (preferably composition ratio 0.6: 0.4 to 0: 1.
0, more preferably 0.5: 0.5 to 0.1:
It is 0.9. ) And other polymer blends may be used.

Preferred specific examples of the polyester derivative used in the present invention are shown below, but the present invention is not limited thereto. Example of polyester compound (() represents a molar ratio.) Homopolymer PET: [terephthalic acid (TPA) / ethylene glycol (EG) (100/100)] Tg = 80 ° C. PEN: [2,6-naphthalenedicarboxylic acid] 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 ℃ PBC-9 TPA / EG / BP (100/20/80) Tg = 115 ℃ PBC-10 PHBA / EG / TPA (200/100/100) Tg = 125 ℃ ・ Polymer blend (weight ratio in () 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 = 142 ° 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 ° C. PBB-7 TPA / 5-sulfoisophthalic acid (SIP) / EG (95/5/100) Tg = 65 ° C. PBB-8 PEN / SIP / EG (99/1/100) Tg = 115 ℃

These supports of the present invention have a thickness of 50 μm to 3 μm.
It has a thickness of 00 μm. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying.
If it exceeds 0 μm, it is inconsistent with the purpose of reducing the thickness for compactness. The thickness is more preferably 50 to 200 μm, further preferably 80 to 115 μm, and particularly preferably 85 to
It is 105 μm. All of the polyesters of the present invention as described above have a flexural modulus higher than that of TAC, and it was possible to realize the original thinning of the film. However, among these, PET has particularly strong flexural elasticity.
PEN is used, and it is possible to reduce the film thickness of 122 μm required for TAC to 105 μm or less.

An ultraviolet absorber may be kneaded into the support used in the present invention for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber does not have absorption in the visible region, and the addition amount thereof is usually 0.5% by weight to 20% by weight, preferably about 1% by weight to 10% by weight based on the weight of the polymer film. Is. 0.5% by weight
If it is less than the above, the effect of suppressing the deterioration of ultraviolet rays cannot be expected. 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 as an ultraviolet absorber
-Hydroxy-4-n-octoxybenzophenone, 4
-Dodecyloxy-2-hydroxybenzophenone,
Benzophenone-based compounds such as 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'
Examples thereof include benzotriazole-based UV absorbers such as -di-t-butyl-5'-methylphenyl) benzotriazole and salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

Polyester derivatives, particularly aromatic polyesters, have a high refractive index of 1.6 to 1.7, whereas gelatin, which is the main component of the photosensitive layer coated on the polyester derivative, has a refractive index of 1.50 to 1.50. Since the value is 1.55, which is smaller than this value, when light is incident from the edge of the support, it is reflected at the interface between the base and the emulsion layer to cause a so-called light piping phenomenon (edge covering). In order to avoid such a light piping phenomenon, a method of adding inert inorganic particles and the like to the support and a method of adding a dye are known. The method of adding a dye is preferable because it does not significantly increase the haze of the support. Regarding the dye used for dyeing the support, the color tone is preferably gray dyeing due to the general properties of the light-sensitive material, excellent in heat resistance in the film-forming temperature range of the polyester support, and excellent in compatibility with polyester. Those are preferable. As a dye,
From the above viewpoint, 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.

The polyester support according to the invention has uses
It is also possible to add slipperiness according to
Kneading organic compounds, applying a surfactant, etc.
Used as a general method. S as an inert inorganic particle
iO₂, TiO₂, BaSO_Four, CaCO₃,talc,
Kaolin and the like are exemplified. Also, as above
For the external particle system in which inert particles are added to the tellur synthesis reaction system
Addition during the polymerization reaction of polyester in addition to the lubricity provided by
To provide slipperiness by internal particle system that deposits the catalysts
The law can also be applied. As a method for imparting slipperiness, polyester
SiO having a refractive index relatively close to that of the support ₂, Or analysis
Internal particles that can make the particle diameter to be relatively small
It is desirable to select the system. Furthermore, by kneading
In some cases, a function was added to obtain more film transparency.
A method of stacking layers is also preferable. Concrete as this means
Has multiple extruders and feedblocks,
Or co-extrusion method with multi-manifold die
To be done.

Next, the surface treatment of the support used in the present invention will be described. A photographic layer (eg, a light-sensitive silver halide emulsion layer,
In order to firmly adhere the intermediate layer, filter layer, conductive layer, etc.), chemical treatment, mechanical treatment, corona treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow treatment, active plasma treatment, laser treatment, mixed acid It is effective to apply the photographic layer directly after the surface activation treatment such as treatment or ozone oxidation treatment, or to apply the photographic emulsion layer on the undercoat layer after the surface treatment is performed once. (For example, US Pat. Nos. 2,698,241, 2,764,520, 2,864,755, 3,462,335, 3,475,193, and 3,143). , 421, 3,501,301, 3,460,944, 3,674,531, British Patents 788,365, 804,005, 89.
No. 1,469, Japanese Patent Publication No. 48-43122, No. 51-4
No. 46). As the surface treatment of the support, corona treatment, ultraviolet treatment, glow treatment, and flame treatment are particularly effective among the above treatments, and the most effective treatment is glow treatment.

Examples of corona treatment, ultraviolet treatment, glow treatment, and flame treatment will be shown below, but the present invention is not limited thereto. The corona 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, in order to improve the wettability of ordinary polyester derivatives, 0.001 KV ・ A ・
Min / m ^{2 to 5} KV ・ A ・ min / m ² , preferably 0.01 KV ・ A
・ Minute / m ^{2 to 1} KV · A ・ Minute / m ² is suitable. Gap clearance between electrode and dielectric roll is 0.5-2.5m
m, preferably 1.0 to 2.0 mm is suitable. For example, a solid state corona processor 6 manufactured by Pillar
When using the KVA model, the discharge frequency during processing is
It is 5 to 40 KHz, and more preferably 10 to 30 KHz. The waveform is preferably an AC sine wave. The gap clearance between the electrode and the dielectric roll is 1 to 2 mm, more preferably 1.4 to 1.6 mm. Moreover, the processing amount is from 0.3 to
0.4 KV · A · min / m ² , more preferably 0.34 to
It is 0.38 KV · A · min / m ² .

Next, the ultraviolet treatment will be described. UV treatment is performed in Japanese Examined Patent Publication No. 43-2603 and Japanese Examined Publication No. 43-2604.
It is preferable to carry out the treatment method described in JP-B-45-3828. The mercury lamp is a high-pressure mercury lamp or a low-pressure mercury lamp composed of a quartz tube, and it is preferable that the wavelength of ultraviolet rays is 180 to 320 nm. The ultraviolet treatment is preferably performed during the film forming step (stretching step, heat setting, after heat setting), and specifically, it is preferably performed in the latter half of the stretching step or at the time of heat setting. 150 if heat fixing
Since the irradiation treatment is carried out at a high temperature of from ℃ to 250 ℃, it is advantageous that the purpose can be achieved with an irradiation time of 1/2 to 2/3 as compared with the irradiation after heat setting. About the method of UV irradiation, 365nm
With a high-pressure mercury lamp whose main wavelength is
1 to 10,000 (mJ / cm ² ) is preferable, and more preferably 50 to
It is 2000 (mJ / cm ² ). In the case of a low-pressure mercury lamp whose main wavelength is 254 nm, the irradiation light amount is 100 to 10,000.
(MJ / cm ² ) is good, more preferably 300 to 1500
(MJ / cm ² ).

Next, glow processing will be described. The glow treatment is a conventionally known method, for example, Japanese Patent Publication No. 35-75.
No. 78, No. 36-10336, No. 45-22004.
No. 45-22005, No. 45-24040, No. 46-43480, JP-A No. 53-129262, US Pat. No. 3,057,792, and No. 3,057,795.
Issue 3, Issue 3,179,482, Issue 3,288,638
No. 3,309,299, No. 3,424,735
No. 3, 3,462,335, 3,475,307
No. 3, No. 3,761,299, No. 4,072,769,
British patents 891,469 and 997,093, etc. can be used. In the glow treatment of the present invention, the most excellent adhesion effect can be obtained especially when water vapor is introduced into the atmosphere. Further, this method is also very effective for suppressing yellowing of the support and preventing blocking.

The partial pressure of water vapor when the glow treatment is carried out in the presence of water vapor is preferably 10% or more and 100% or less,
More preferably, it is 40% or more and 90% or less. If it is less than 10%, it becomes difficult to obtain sufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like. A method for quantitatively introducing water vapor into the glow discharge treatment atmosphere is to use a quadrupole mass spectrometer (Nippon Vacuum M
SQ-150) and conduct it while quantifying the composition. Furthermore, when performing vacuum glow treatment while heating the support to be surface-treated, it is possible to improve the adhesiveness in a shorter time than the treatment at room temperature and to significantly reduce the yellowing of the support. it can. The preheating described here is different from the heat treatment for improving the winding tendency described later. The preheating temperature is preferably 50 ° C. or higher and Tg or lower, more preferably 70 ° C. or higher and Tg or lower, and further preferably 90 ° C. or higher and Tg or lower.
Preheating at a temperature of Tg or higher deteriorates adhesion. Specific methods for raising the surface temperature of the support in vacuum include heating with an infrared heater and heating with contact with a hot roll. A widely known heating method can be used as the heating method. In the glow treatment, it is preferable that a plurality of electrodes each having a hollow portion that serves as a refrigerant flow path are disposed so as to face each other in the width direction of the film, and the treatment is performed while the support is being transported.

The degree of vacuum during the glow treatment is 0.005 to 20.
Torr is preferred. More preferably 0.02 to 2
It's Torr. If the pressure is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained. On the other hand, if the pressure is too high, stable discharge does not occur.
Further, the voltage is preferably between 500 and 5000V. More preferably, it is 500-3000V. If the voltage is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained. On the other hand, if the voltage is too high, the surface will be deteriorated, and conversely the adhesiveness will decrease. Also,
The discharge frequency used is from direct current to several 1000 MHz, preferably 50 Hz to 20 M, as found in the prior art.
Hz, and more preferably 1 KHz to 1 MHz. Discharge treatment intensity is 0.01 KV · A · min / m ^{2 to 5} KV · A
・ Min / m ² is preferable, more preferably 0.15 KV · A
Desired adhesive performance at · min / m ² ~1KV · A · min / m ^2.

It is preferable that the temperature of the support thus subjected to the glow treatment is immediately lowered by using a cooling roll. The support is likely to be plastically deformed by an external force as the temperature rises, and the flatness of the support is impaired. Furthermore, low-molecular weight substances (monomers, oligomers, etc.) may be deposited on the surface of the support, which may deteriorate transparency and blocking properties. The flame treatment method may be natural gas or liquefied propane gas, but the mixing ratio with air is important. In the case of propane gas, the preferable mixing ratio of propane gas / air is 1/14 to 1/22, preferably 1/16 to 1/19 by volume. In the case of natural gas, it is 1/6 to 1/10, preferably 1/7 to 1/9. The flame treatment may be performed in the range of 1 to 50 Kcal / m ² , more preferably 3 to 20 Kcal / m ² . It is more effective if the distance between the tip of the internal flame of the burner and the support is less than 4 cm. A frame processing device manufactured by Kasuga Electric Co., Ltd. can be used as the processing device. Further, the backup roll that supports the support during the flame treatment is a hollow roll, and it is preferable that the backup roll is water-cooled by cooling water and always treated at a constant temperature.

Next, the undercoat layer provided between the surface-treated support of the present invention and the photographic layer will be described. As the undercoat layer, a layer that adheres well to the support as the first layer (hereinafter abbreviated as the undercoat first layer) is provided, and a layer that adheres the undercoat first layer and the photographic layer as the second layer thereon There is a so-called multi-layer method in which an undercoating second layer is abbreviated), and a single layer method in which only one layer which adheres a support and a photographic layer well is applied.
In the first undercoat layer in the multi-layer method, for example, a single layer selected from vinyl chloride, vinylidene chloride, butadiene, vinyl acetate, styrene, acrylonitrile, methacrylic acid ester, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. A copolymer having a monomer as a starting material, an epoxy resin, gelatin, nitrocellulose, polyvinyl acetate and the like are used. (For these, EHImmerg
ut “Polymer Handbook” a 187-231, Interscien
See Se Pub. New York 1966 etc.). Gelatin is mainly used in the second undercoat layer.

In the single layer method, a method is often used in which the support is swollen and interfacially mixed with the undercoat polymer to obtain good adhesiveness. This undercoat polymer, gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, water-soluble polymers such as maleic anhydride copolymers, carboxymethyl cellulose,
Cellulose ester such as hydroxyethyl cellulose,
A latex polymer such as a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylic acid ester-containing copolymer, a vinyl acetate-containing copolymer, a vinyl acetate-containing copolymer and the like are used. Of these, gelatin is preferred. As gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, modified gelatin, and the like commonly used in the art can be used. Among these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used. These gelatins contain various impurities such as 0.01 to 20 in the production process.
000ppm of metals (Na, K, Li, Rb, Ca,
Mg, Ba, Ce, Fe, Sn, Pb, Al, Si, T
metals such as i, Au, Ag, Zn, Ni, and their ions), ions (F, Cl, Br, I, sulfate ions,
Nitrate ion, acetate ion, ammonium ion, etc.) may be contained. In particular, it is common knowledge in the art to contain Ca and Mg ions in lime-processed gelatin, and the content thereof is very wide, from 10 to 3000 ppm, but 1000 ppm or less is preferable in view of undercoat coating performance, and more preferably 500 ppm or less. is there.

In the case of a synthetic hydrophilic compound, other components may be copolymerized, but when the amount of the hydrophobic copolymerization component is too large, the moisture absorption amount and the moisture absorption rate of the non-photosensitive hydrophilic layer become small, and the curl is taken into consideration. Out of place. These hydrophilic compounds may be used alone or in combination of two or more. The primer polymer described above can be cured. Examples of the hardener include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), epoxy compounds, isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-).
Triazine, etc.), epichlorohydrin resin, polyamide-epichlorohydrin resin (Japanese Patent Publication No. Sho 49-2658).
0, JP-A-51-3619) and cyanuric chloride compounds (for example, JP-A-47-6151 and JP-A-47-33).
380, 54-25411, JP-A-56-130.
No. 740), vinyl sulfone or sulfonyl compounds (for example, JP-B-47-24259).
No. 50-35807, JP-A-49-24435.
Nos. 53-41221 and 59-18944), and carbamoyl ammonium salt compounds (for example, Japanese Examined Patent Publication Nos. 56-12853 and 58-32).
699, JP-A-49-51945, 51-596.
25, 61-9641, and amidinium salt compounds (for example, JP-A-60-22514).
8) and carbodiimide compounds (for example, JP-A-51-126125 and JP-A-52-48311).
Compounds described in JP-A-58-50699, JP-A-52-5442.
7, JP-A-57-44140 and 57-46538.
No. 825,7)
26, U.S. Pat. No. 3,321,313, JP-A-50.
-38540, 52-93470, 56-43.
Examples thereof include compounds described in Nos. 353 and 58-113929.

The undercoat layer of the present invention may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. Further, the undercoat layer of the present invention may contain inorganic or organic fine particles as a matting agent to such an extent that the transparency and graininess of an image are not substantially impaired. As a matting agent for inorganic fine particles, silica (SiO ₂ ), titanium dioxide (TiO ₂ ), calcium carbonate, magnesium carbonate, etc. can be used. As the organic fine particle matting agent, polymethylmethacrylate, cellulose acetate propionate,
Polystyrene, soluble in the treatment liquid described in US Pat. No. 4,142,894, US Pat. No. 4,39
Polymers described in No. 6,706 can be used. The average particle size of these fine particle matting agents is 0.
It is preferably from 01 to 10 μm. More preferably,
It is 0.05 to 5 μm. Moreover, the content is 0.5-
600 mg / m ² is preferable, and 1 to 400 is more preferable.
It is mg / m ² . As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, Monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, chloral hydrate and the like are used. Of these, preferred are resorcin and p-chlorophenol.

The undercoating liquid relating to the present invention is generally well-known coating methods such as dip coating method, air knife coating method, curtain coating method, roller coating method,
It can be applied by a wire bar coating method, a gravure coating method, an extrusion coating method using a hopper described in US Pat. No. 2,681,294, or the like. Also, as required, US Pat.
1,791, 3,508,947, 2,941,8
No. 98 and No. 3,526,528, Yuji Harazaki, “Coating Engineering”, page 253 (published by Asakura Shoten in 1973) and the like can be used to simultaneously coat two or more layers. Next, a heat treatment method for improving the curl of the support of the present invention will be described. In general, a polyester support is rapidly cooled from Tg or higher to Tg or lower after film formation, stretching and heat setting, and is fixed while maintaining a large free volume at Tg or higher, so that a curling tendency is likely to occur. However, by carrying out the heat treatment described here, the free volume in the support can be reduced and the curl can be made less likely to occur.

The heat treatment temperature is Tg to (Tg-50 ° C.),
It is more preferably Tg to (Tg-30 ° C), and further preferably Tg to (Tg-20 ° C). When the heat treatment temperature exceeds the glass transition temperature, the support becomes easy to curl.
If the temperature is lower than (Tg-50 ° C), it takes a long time to obtain a sufficient curling habit improving effect, resulting in poor industrial productivity. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. Average cooling rate is -0.01-
20 ° C./hour, more preferably −0.1 to −5 ° C./hour. This heat treatment time is 0.1 to 1500 hours,
More preferably 0.5 to 500 hours, still more preferably 1
~ 200 hours. If the time is 0.1 hours or less, a sufficient effect cannot be obtained, and if the time is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. When the thus heat-treated support is measured with a differential thermal analyzer, an endothermic peak appears near Tg, and the larger the endothermic peak, the more the winding tendency is less likely to occur, and 100 mcal / g or more, more preferably 200 mcal / g. It is preferable that the heat treatment is performed as described above.

In order to further increase the effect of eliminating the curling habit, after the heat treatment is performed at a temperature not lower than Tg and lower than the melting point (melting temperature determined by DSC) before the heat treatment, the heat history of the support is erased. The heat treatment may be performed at the temperature of Tg to (Tg-50 ° C). In the present invention, this heat treatment is called "pre-heat treatment", and the heat treatment of Tg to (Tg-50 ° C) described in the preceding paragraph is called "post-heat treatment" to distinguish them. Pre-heat treatment temperature is T
g or more and less than melting point is preferable, more preferably Tg + 10
℃ or higher and crystallization temperature (crystallization temperature determined by DSC) or lower,
More preferably, it is performed at Tg + 20 ° C. or higher and the crystallization temperature or lower. If the pre-heat treatment is performed at a temperature equal to or higher than the melting point, the elasticity of the support is remarkably reduced, causing surface failure and transport failure. The pre-heat treatment may be carried out within this temperature range at a constant temperature (constant temperature pre-heat treatment), may be carried out while lowering the temperature (pre-heat treatment before cooling), or may be carried out while raising the temperature (rise of temperature). Pre-heat treatment). The pre-heat treatment time is preferably 0.1 minutes or more and 1500 hours or less, more preferably 1 minute or more and 10 hours or less, and further preferably 1 minute or more and 1 hour or less. If it is 0.1 minutes or less, a sufficient effect cannot be obtained, and if it is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. After this pre-heat treatment, a post-heat treatment is carried out, but it may be rapidly cooled from the pre-heat treatment end temperature to the post-heat treatment start temperature, or may be gradually cooled to the post-heat treatment start temperature across Tg. Alternatively, the temperature may be once cooled to room temperature and then raised to the post-heat treatment temperature. Although there are several combinations of these pre-heat treatment and post-heat treatment methods, after the constant temperature pre-heat treatment at Tg + 20 ° C. or higher and the crystallization temperature or lower, a cooling rate of −0.1 to Tg−20 ° C. A post-heat treatment is preferably performed while cooling at -5 ° C / hour.

The heat treatment of such a support may be carried out in the form of a roll (A) or while being conveyed in the form of a web (B). When heat-treated in the form of a roll (A), a method of heat-treating the roll from room temperature in a constant temperature bath,
Any method may be used, in which the web is heated to a predetermined temperature during the web conveyance and then wound into a roll and subjected to heat treatment. Although the method of (1) requires a long time for raising and lowering the temperature, it has an advantage of requiring less equipment investment. The method of (1) requires winding equipment at high temperature, but has an advantage that the heating time can be omitted. In the roll-shaped heat treatment, due to the heat shrinkage stress generated during the heat treatment, wrinkles due to winding tightness and surface defects such as cut-outs of the core portion are likely to occur. Therefore, unevenness is imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ doped with Sb ₂ O ₅ are applied) to reduce creaking between the supports to prevent wrinkles due to winding tightening. , At the end of the support
It is desirable to take measures such as preventing the cut end of the winding core from being exposed by providing a let and slightly raising only the end.
On the other hand, when the heat treatment is performed in the web form (B), a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the roll form. Among these heat treatment methods, it is preferable that the pre-heat treatment is performed in a web shape and the post-heat treatment is performed in a roll shape. This is because when the pre-heat treatment is performed in the form of a web, planar defects are less likely to occur than when the pre-heat treatment is performed in the form of a roll, and the post-heat treatment requires a relatively long time. Further, the roll core used in the heat treatment is preferably one having a built-in electric heater or a structure capable of flowing a high-temperature liquid so that the film can be hollow or heated for efficient temperature propagation to the film. . The material of the roll core is not particularly limited, but it is preferable that the core does not undergo strength reduction or deformation due to heat, such as stainless steel,
A resin containing glass fiber can be mentioned.

These heat treatments may be carried out at any stage after the film formation of the support, the surface treatment of the support, the coating of the back layer (antistatic agent, lubricant, etc.), and the coating of the undercoat. Preferred is after the antistatic agent is applied. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment. Next, the spool preferably used in the present invention will be described. The present invention is to provide a silver halide photographic light-sensitive material having a smaller Batrone than ever before. The most effective way to miniaturize a batrone is to reduce the diameter of the spool on which the film is wound. The diameter of the spool that can be used in the present invention is 5 to 10 mm. Conventional spool has a diameter of 11.5
Since it is mm, the cartridge can be significantly downsized. The spool diameter preferably used in the present invention is 6 to 9 mm, more preferably 7 to 8 mm. If the spool diameter is larger than 10 mm, there is not much merit in miniaturizing the cartridge. On the other hand, if it is less than 5 mm, the emulsion layer of the light-sensitive material is greatly distorted and the silver halide is exposed to pressure. Next, the slip agent preferably used in the present invention will be described. Examples of the slip agent used in the present invention include Japanese Patent Publication No. 53-2.
No. 92, polyorganosiloxanes, higher fatty acid amides as disclosed in US Pat. No. 4,275,146, Japanese Patent Publication No. 58-335.
No. 41, British Patent No. 927,446, or JP-A Nos. 55-126238 and 58-90633, higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and 10 carbon atoms). .About.24 alcohol ester) and US Pat. No. 3,933,516.
Higher fatty acid metal salts as disclosed in JP-A-58-50534, and
Esters of straight chain higher fatty acids and straight chain higher alcohols, higher fatty acid-higher alcohol esters containing a branched alkyl group as disclosed in WO 90108115.8 and the like are known.

Among these, as polyorganosiloxane, there are generally known polyalkylsiloxanes such as polydimethylsiloxane polydiethylsiloxane, polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, and Japanese Patent Publication 53-
292, JP-B-55-49294, JP-A-60-140
341, etc., such as an organopolysiloxane having a C5 or higher alkyl group, an alkylpolysiloxane having a polyoxyalkylene group in its side chain, and an alkoxy, hydroxy, hydrogen, carboxyl, amino, or mercapto group in its side chain. It is also possible to use modified polysiloxanes such as organopolysiloxanes, block copolymers having siloxane units, and JP-A-60-1.
It is also possible to use a graft copolymer having a siloxane unit in the side chain as shown in 91240. or,
Examples of higher fatty acids and their derivatives, higher alcohols and their derivatives include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, higher fatty acid polyhydric alcohol esters, and higher aliphatic alcohols.
Monoalkyl phosphite of higher aliphatic alcohol,
Dialkyl phosphite, trialkyl phosphite, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, its amide compound, or its salt can be used.

As represented by the general formulas (1) and (2),
The long-chain alkyl compound is preferable in that sufficient slip properties and scratch resistance can be obtained before and after the development treatment. General formula (1) R ¹ X ¹ R ² General formula (2) R ³ X ² R ⁴ X ³ R ^{5 In} this general formula (1), R ¹ and R ² are aliphatic hydrocarbon groups. The total carbon number of this compound is 25 or more and 120
You need the following: The total number of carbons needs to be 25 or more in order to obtain sufficient slipperiness. Also, the total carbon number is 120
When the amount is larger, the solubility in an organic solvent is poor, and it becomes difficult to apply it by dispersion or coating. The total carbon number is more preferably 30 or more and 100 or less, further preferably 40 or more and 80 or less. Further, R ¹ and R ² are sufficient scratch resistance,
Also, in order to suppress deterioration of slipperiness under various use conditions, it is preferable that each is an aliphatic hydrocarbon group having 10 to 70 carbon atoms. When the carbon number is 10 or less, the scratch resistance is deteriorated, and the sliding property is deteriorated by the transfer of the lubricant under various use conditions. Further, one-terminal functionalized aliphatic compounds having 70 or more carbon atoms are not generally known. This aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable from the viewpoint of scratch resistance. The carbon number of R ¹ and R ² is more preferably 15 or more and 50 or less.

In the general formula (2), R³, R^Four, R^Five
Is an aliphatic hydrocarbon group. The total carbon number of this compound is 3
It must be 0 or more and 150 or less. Sufficient slip of total carbon
In order to obtain the property, 30 or more is required. Also, total charcoal
If the number of primes exceeds 150, the solubility in organic solvents
Poor, it becomes difficult to apply by dispersion or coating. Total carbon number and
And more preferably 40 or more and 130 or less, and more preferably
Or more than 50 and less than 120. Also, sufficient scratch resistance,
And to prevent deterioration of slipperiness under various usage conditions, R
³, R^FiveAre each aliphatic having 10 to 70 carbon atoms
Hydrocarbon group, R ^FourIs an aliphatic having 10 to 50 carbon atoms
It is preferably a hydrocarbon group. R³, R^Fiveabout
When the carbon number is 10 or less, the scratch resistance deteriorates, and
Under the conditions of use, the slippery transfer causes deterioration of slipperiness.
It In addition, a fat having a carbon number of 70 or more and functionalized at one end
Family compounds are generally unknown. This aliphatic carbonization
The hydrogen group may have a straight-chain structure or contain an unsaturated bond.
May have some substituents, may have a branched structure
You may have a structure. Among them, especially from the viewpoint of scratch resistance
A linear structure is preferred. R³, R^FiveOf carbon number
Particularly preferred is 15 or more and 50 or less. Well
R^FourFor, if the carbon number is 10 or less, scratch resistance
Is deteriorated, and the slipperiness due to the transfer of the lubricant under various usage conditions
Worsens. In addition, functional groups with both ends having 50 or more carbon atoms
Modified aliphatic compounds are generally unknown. This
The aliphatic hydrocarbon group may also have a linear structure,
It may contain unsaturated bonds, or may have some substituents
It may have a branched structure. This
From the viewpoint of scratch resistance, a linear structure is particularly preferable.
R^FourIt is preferable that the number of carbon atoms in the
Is. Particularly preferred is 12 or more and 25 or less.

In the general formulas (1) and (2), X
¹ , X ² and X ³ are divalent linking groups. Specifically, -C
(O) O -, - C (O) NR -, - SO 3 -, -OSO 3 -, -SO 2 NR-, -O-,
-S-, -NR-, -OC (O) NR- and the like are shown (R represents H or an alkyl group having 8 or less carbon atoms). Specific examples of the compounds represented by the general formulas (1) and (2) are shown below.

(1-1) n-C ₁₅ H ₃₁ COOC ₃₀ H ₆₁ -n (1-2) n-C ₁₇ H ₃₅ COOC ₄₀ H ₈₁ -n (1-3) n-C ₁₅ H ₃₁ COOC ₅₀ H ₁₀₁ -n (1-4) n-C ₂₇ H ₄₃ COOC ₂₈ H ₅₇ -n (1-5) n-C ₂₁ H ₄₃ COOCH ₂ CH (CH ₃ )-
C ₉ H ₁₉ (1-6) n-C ₂₁ H ₄₃ COOC ₂₄ H ₄₉ -iso

(2-1) n-C ₂₉ H ₄₉ OCO (CH ₂ )
₂ COOC ₂₄ H ₄₉ -n (2-2) n-C ₁₈ H ₃₇ OCO (CH ₂ ) ₄ COOC ₄₀
H ₈₁ -n (2-3) n-C ₁₈ H ₃₇ OCO (CH ₂ ) ₁₈ COOC ₁₈
H ₃₇ -n (2-4) iso-C ₂₄ H ₄₉ OCO (CH ₂ ) ₄ COOC
₂₄ H ₄₉ -n (2-5) n-C ₄₀ H ₈₁ OCO (CH ₂ ) ₂ COOC ₅₀
H ₁₀₁ -n (2-6) n-C ₁₇ H ₃₅ COO (CH ₂ ) ₆ OCOC ₁₇
H ₃₅ -n (2-7) n-C ₂₁ H ₄₃ COO (CH ₂ ) ₁₈ OCOC ₂₁
H ₄₃ -n (2-8) iso-C ₂₃ H ₄₇ COO (CH ₂ ) ₂ OCOC
₂₃ H ₄₇ -n (2-9) iso-C ₁₅ H ₃₁ COO (CH ₂ ) ₆ OCOC
₂₁ H ₄₃ -n

The polyether-containing compound used in the present invention as described above is obtained, for example, by sequentially adding ethylene oxide to a corresponding higher alcohol by a conventional method, or by adding this higher alcohol polyether to a corresponding dicarboxylic acid. It can be easily synthesized by dehydration condensation of the product or condensation of a higher carboxylic acid with the higher alcohol polyether adduct. More preferred slipping agents are compounds having a polar substituent in at least one of R ¹ and R ^{2 in} the general formulas (1) and (2) or in at least one of R ³ , R ⁴ and R ⁵ . Is. The polar substituent here means a group capable of forming a hydrogen bond or an ionic dissociative group. The polar substituent is not particularly limited, -OH, -COOH, -COOM, -NH _3,
—NR ₄ ⁺ A ⁻ , —CONH _{2 and the} like are preferable. here,
M is a cation such as an alkali metal, an alkaline earth metal or a quaternary ammonium salt, R is H or a hydrocarbon group having 8 or less carbon atoms, and A ⁻ is an anion such as a halogen atom. Also,
Of these groups, -OH is particularly preferred. Any number of the polar substituents may be contained in one molecule. The amount of the slip agent represented by the general formulas (1) and (2) of the present invention is not particularly limited, but its content is 0.001 to 0.1 g in order to exhibit sufficient slip and scratch resistance. / M ² is preferable, and more preferably 0.005 to 0.05 g / m ² . Specific examples will be given below, but the present invention is not limited thereto.

(3-1) HOCO (CH ₂ ) ₁₀ COOC ₂₁ H ₄₃ (3-2) C ₁₇ H ₃₅ COOCH ₂ CH (OH) C ₁₂ H
₂₅ (3-3) C ₉ H ₁₉ C (OH) (C ₉ H ₁₉ ) CH ₂ C
OOC ₂₅ H ₅₁ (3-4) C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COO
_{C 40 H 61 (3-5) C} 14 H 29 CH (NH 2) COO (CH 2)
_{n CH (CH 3) (CH} 2) m -CH
(N + m = 15) ( 3-6) CH 3 (CH 2) 2 CH (COONa) (CH
₂ ) ₆ COOC ₄₀ H ₈₁ (3-7) HOCH ₂ (CH ₂ ) ₆ CH (OH) CH (O
_{H) (CH 2) 4 COO} -C 50 H 101 (3-8) C 17 H 33 COO (CH 2) 16 OH (3-9) CH 3 (CH 2) 2 CH (OH) (CH 2) 6 C
ONHC ₂₁ H ₄₂ (3-10) C ₇ H ₁₅ -φ-COOCH (CONH ₂ )
C ₁₆ H ₃₃ (3-11) C ₂₇ H ₅₅ COOCH ₂ CH (OH) CH _{2
OH (3-12) HOCO (CH 2} ) 5 COOC 40 H 81 (3-13) CH 3 (CH 2) 15 CH (SO 3 Na) COO
_{CH 2 CH (C 13 H 27} ) -C 10 H 21

(4-1) C ₁₄ H ₂₉ CHCOO (CH ₂ ).
₅ OCOCH (OH) C ₁₄ H ₂₉ (4-2) C ₁₀ H ₂₁ COOCH (C ₂ H ₅ ) (CH ₂ ) _{7
CH (C 2 H 4 COOH)} -OCOC 10 H 21 (4-3) NaOCO (CH 2) 11 COO (CH 2) 10 O
_{CO (CH 2) 11 -COOH (} 4-4) C 9 H 19 C (OH) (C 9 H 19) CH 2 C
_{OO (CH 2) 15 CONH-} C 10 H 21 (4-5) H 2 NCO (CH 2) 10 COOCH (C 6 H
_{13) (CH 2) 10 COO} -C 30 H 61 (4-6) C 14 H 29 CH (N + (CH 3) 4 Cl -) C
_{OO (CH 2) 10 OCO-} C 17 H 33 (4-7) C 6 H 13 CH (OH) (CH 2) 10 COO
_{(CH 2) 8 OCO- (CH} 2) 10 CH (OH) C 6 H 13 (4-8) C 15 H 31 COOCH 2 CH (OH) CH 2
OCOC ₁₅ H ₃₁ (4-9) C ₈ H ₁₇ NHCO (CH ₂ ) ₁₀ COO (C
H ₂ ) ₁₅ OH (4-10) C ₄₀ H ₈₁ OCO (CH ₂ ) ₅ COO (CH
₂ ) ₅ COOH (4-11) CH ₃ (CH ₂ ) ₁₅ CH (SO ₃ Na) COO
_{(CH 2) 2 CH (CH} 3) - (CH 2) 2 OCOC 17 H 35 (4-12) HOCH 2 CH (OH) CH 2 OC (CH
_{2) 3 CH (C 2 H} 5) - (CH 2) 9 COOC 50 H 101 φ: -C 6 H 4 -

Since the compounds of the above-mentioned general formula have high hydrophobicity, they often have poor solubility in solvents. Therefore, there is a method of dissolving in a non-polar organic solvent such as toluene or xylene or a method of dispersing in a coating liquid, but the method of dispersing is preferable because the non-polar organic solvent is difficult to handle. At this time, any dispersant may be used as long as it does not deteriorate slipperiness and scratch resistance, but preferable dispersants include those described in the following general formula (3). General formula (3) R ⁶ YBD In the general formula (3), R ⁶ is an aliphatic hydrocarbon group having 25 or more and 70 or less carbon atoms. This hydrocarbon group may contain an unsaturated bond, may be substituted with various substituents, and may contain a branched structure. A straight-chain aliphatic hydrocarbon group is particularly preferable in terms of slipperiness and scratch resistance. The carbon number of this hydrocarbon group is in the range of 25 or more and 70 or less. A hydrocarbon group having 25 or less carbon atoms causes problems such as sufficient slippage, scratch resistance not being exhibited, and deterioration of slipperiness after treatment. As a hydrocarbon compound having a carbon number of 70 or less and having one end functionalized, a long-chain linear or branched aliphatic alcohol or the like is known.
Compounds having 0 or more hydrocarbon groups are generally unknown. Particularly preferred as carbon number is 3
It is 0 or more and 60 or less.

Y is a divalent linking group. Specifically
Is -C (O) O-, -OCO-, -C (O) NR'-, -NR'CO-, -SO₂NR'-,
-NR'SO₂-, -O-, -S-, -NR-, -OCOR''COO-, -OCO
R''O- and the like can be mentioned (R 'is H or 8 carbon atoms.
The following hydrocarbon groups are shown. R '' is from 0 carbons
Shows up to 8 hydrocarbon groups). Also, B is-(CH₂CH₂O)
_a-, Or- (CH₂CH (OH) CH₂O)_b-, Or-((CH₂) _cC
H (R) CH₂O)_d-, Or- (CH₂CH₂O)_e-(CH₂CH (OH) CH₂O)
_f-((CH₂)_cCH (R) CH₂O)_g-From any of the units
, A is 3-40, b, d is 3-30, c is 1-3,
e is 0 to 40, f and g are 0 to 30, and e + f + g is
3-40, R is H, CH₃, A phenyl group. these
If the length of the nonionic group of the
Sufficient dispersion when solubility is not obtained or when dispersed
Stability cannot be obtained. Also, if it is too long, it will have sufficient slip and
Scratch does not appear, deterioration of slipperiness over time after treatment
Problems such as happening occur. Of the above nonionic groups,
Preferred for-(CH₂CH₂O)_a-And a is preferably
Is 5 to 30. This general formula (3) anti-slip agent (1)
The use ratio of (2) is preferably 1: 9 to 9: 1.
More preferably, it is 6: 4 to 2: 8. Also, the amount of slip agent
The dispersion method will be described later. It is expressed by this general formula (3)
Specific examples of the compound are shown below.

(5-1) n-C ₃₀ H ₆₁ O (CH ₂ CH ₂ O) ₁₀ H (5-2) n-C ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₅ H (5-3) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (5-4) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₃₀ H (5-5) n-C ₄₀ H ₈₁ O ( _{CH 2 CH 2 O) 10 H} (5-6) n-C 50 H 101 (CH 2 CH 2 O) 16 H (5-7) n-C 50 H 101 - (CH (CH 3) CH 2 O) _{3
(CH 2 CH 2 O) 16} H (5-8) n-C 50 H 101 - (CH 2 CH (OH) CH 2
_{O) 3 - (CH (OH} ) CH 2 O) 3 - (CH 2 CH 2
O) ₁₅ H (5-9) n-C ₄₀ H ₈₁ OCOCH ₂ CH ₂ COO (C
_{H 2 CH 2 O) 16 H} (5-10) n-C 50 H 101 OCOCH = CHCOO (C
_{H 2 CH 2 O) 16 H} (5-11) n-C 50 H 101 OCOCH 2 CH 2 COO-
_{(CH 2 CH (OH) CH} 2 O) 3 - (CH 2 CH
₂ O) ₁₅ H

The use of a binder capable of forming a film in the layer containing the compounds of the general formulas (1), (2) and (3) improves the surface condition of the lubricant applied and improves the film strength of the lubricant layer. Is particularly preferable in terms of. Examples of such a polymer include known thermoplastic resins, thermosetting resins, radiation curable resins,
Reactive resins, and mixtures thereof, hydrophilic binders such as gelatin can be used. Specific binders include those described above in the matting agent of the present invention.

Some additives may be added to the above-mentioned slip agent layer in order to impart other functions. For example, a surfactant having a sulfonic acid or sulfuric acid ester as a hydrophilic part may be added as an additive in order to improve repellency caused by a hydrophobic slip agent, and examples thereof include compounds represented by the following general formula (4). General formula (4) R ⁷ ZEM ^{1 In} general formula (4), R ⁷ is an aromatic or aliphatic hydrocarbon group. The hydrocarbon group is not particularly limited, but specifically, straight chain alkyl, branched alkyl, substituted or unsubstituted phenyl group, naphthalene group, succinic acid ester of alkyl group, ester of phosphoric acid, etc. can give. Z is a divalent linking group. This linking group may be omitted. The linking group is not particularly limited, but specifically includes -R-, -OR-, -COOR-, -OCOR-, etc., and R is an alkyl group having 0 to 10 carbon atoms, a polyoxyethylene group,
A polyoxypropylene group and the like. Also, E is -OS
O ₃ − and —SO ₃ −. M ¹ is H or a cation such as an alkali metal, an alkaline earth metal or a quaternary ammonium salt. Specific examples of the compound represented by the general formula (4) are shown below.

(6-1) C ₁₂ H ₂₅ OSO ₃ Na (6-2) C ₁₆ H ₃₃ OSO ₃ Na (6-3) C ₁₈ H ₃₇ φSO ₃ Na (6-4) C ₈ H ₁₇ φSO ₃ Na (6-5) C ₁₂ H ₂₅ φSO ₃ Na (6-6) C ₆ H ₁₃ OCOCH ₂ CH (C ₆ H ₁₃ OC
_{O) SO 3 Na φ: -C} 6 H 4 -

The amount of the additive represented by the general formula (4) of the present invention is preferably 0.001 g / m ² or more and up to the solid content of the slip agent, and from 0.005 g / m ² An amount up to 1/2 of the solid content of the agent is more preferable. The above-mentioned slipping agent is coated with a coating liquid prepared by dissolving or dispersing it in a suitable water or organic solvent on a support or a support having another layer on the back surface, or at the time of coating an emulsion, and then dried. It can be formed by As a method of dispersing the slip agent, a generally known emulsification / dispersion method can be used. Specifically, there are a method of dissolving in an organic solvent and emulsifying in water, a method of melting a lubricant at a high temperature and emulsifying in water, a solid dispersion method using a ball mill, a sand grinder, and the like. Such emulsification / dispersion methods are described in textbooks such as "Karimai, Pebble, Hidaka" and "Handbook for Emulsification / Dispersion Technology Application" (Science Forum Edition).

The slip agent used in the present invention may be dispersed in an organic solvent by various methods. As a method for dispersing in an organic solvent, a generally known method can be used. As a preferred method, specifically, a method in which a slip agent is solid-dispersed in an organic solvent by a ball mill, a sand grinder, or the like, a slip agent is heated and dissolved in an organic solvent, and cooling precipitation is performed with stirring. Dispersion method, or a method in which a lubricant is dissolved in an organic solvent by heating and then added to an organic solvent at room temperature or in a cooled state to disperse by cooling and precipitation, and mutually compatible. Not emulsifying with organic solvents. Among these, a preferred method is a method in which the slipping agent is dissolved in an organic solvent by heating, and this is added to an organic solvent at room temperature or in a cooled state, cooled, precipitated and dispersed. The organic solvent used for this dispersion is not particularly limited, but a solvent having a high polarity is preferable as the cooling medium to which the lubricant solution is added. A particularly preferable method is a method in which the lubricant is heated and dissolved at 60 ° C. to 150 ° C. and is dispersed as a cooling medium in a solvent having a solubility of 1% or less at room temperature. Among the solvents in which the solubility of the lubricant at room temperature is 1% or less, ketones and alcohols are particularly preferable because of good dispersibility. Further, as the disperser used in this dispersion, an ordinary stirrer can be used, but an ultrasonic disperser and a homogenizer are particularly preferable.

As the diluting solvent used for coating, any solvent may be used as long as it does not deteriorate the dispersion stability or solubility of the slip agent. For example, water, water containing various surfactants, alcohols (methanol, ethanol). , Isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, and other methyl, ethyl, propyl, butyl esters, etc.), hydrocarbons ( Hexane, cyclohexane, etc.) Halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, toluene, xylene, benzyl alcohol, benzoic acid, anisole, etc.), amides (dimethylformamide, Dimethylacetamide, n-meth Pyrrolidone, etc.), ethers (diethyl ether, dioxane, tetrahydrofuran, etc.), ether alcohols such as propylene glycol monomethyl ether, glycerol, diethylene glycol, dimethyl sulfoxide and the like. Among them, water for handling, water containing various surfactants, alcohols,
Ketones and esters are preferred.

Next, the antistatic agent used in the present invention will be shown. The antistatic agent of the present invention is not particularly limited and may be a conductive antistatic agent or a compound having a charge series adjusting action. Examples of the conductive antistatic agent include metal oxides and ionic compounds. The conductive antistatic agent preferably used in the present invention is a conductive metal whose antistatic property is not deactivated even after development processing. Examples thereof include oxides and their derivatives, conductive metals, carbon fibers, π-conjugated polymers (polyarylene vinylene, etc.), and among them, the conductive material particularly preferably used is crystalline metal oxide particles. Those containing oxygen defects such as crystalline metal oxide particles and those containing a small amount of different atoms forming donors with respect to the metal oxide used are generally preferable because they have high conductivity, and the latter is particularly preferable. It is particularly preferable because it does not give fog to the silver halide emulsion. Examples of metal oxides include
ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In
₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O
Fine particles of at least one crystalline metal oxide selected from ₅ or their composite oxides (acicular, spherical,
Plate-shaped, irregular type). Particularly preferred is Sn
A metal oxide containing O ₂ as a main component and containing about 5 to 20% of antimony oxide, and a metal oxide containing another component (eg, silicon oxide, boron, phosphorus, etc.), Zn
O, TiO ₂ and the like.

The fine particles of these crystalline metal oxides or their composite oxides have a volume resistivity of 10 ⁷ Ω.
cm or less, and more preferably 10 ⁵ Ω · cm or less. Regarding the fine particles of these crystalline metal oxides or their composite oxides, JP-A-56-143430.
No. 60-258541.
These conductive metal oxide fine particles can be prepared by first burning the metal oxide fine particles and then heat-treating them in the presence of different atoms to improve conductivity. Second, burning the metal oxides. There are used a method of coexisting different kinds of atoms during the production of fine particles of particles, a third method of introducing oxygen defects by reducing the oxygen concentration during firing. As a heteroatom, Z
Al and In for nO and N for TiO ₂ .
b, Ta are Sb, Nb, P, B, and SnO ₂ .
Examples include In, V, and halogen. The addition amount of the heteroatom is preferably in the range of 0.01 mol to 30 mol%,
10 mol% is particularly preferred. Furthermore, in order to improve the dispersibility of fine particles and the transparency, a silicon compound may be added during the formation of fine particles.

Further, as described in JP-B-59-6235, a conductive material obtained by adhering the above metal oxide to other crystalline metal oxide particles or fibrous substances (for example, titanium oxide) is used. Good. The primary particle size of the conductive metal oxide that can be used is preferably 0.0001 to 1 μm, but when it is 0.001 to 0.5 μm, stability after dispersion is good and easy to use. Further, it is very preferable to use the conductive particles of 0.001 to 0.3 μm in order to reduce the light scattering property as much as possible because a transparent photosensitive material can be formed. These particles are secondary aggregates in which the particles in the dispersion and the coating film are usually several primary particles or more,
The particle size is 0.5 to 0.005 μm, preferably 0.3 to 0.01 μm, and particularly preferably 0.2 to 0.0.
It is 3 μm. When the conductive material is needle-like or fibrous, the length is preferably 30 μm or less and the diameter is 1 μm or less, and particularly preferably, the length is 10 μm or less and the diameter is 0.3 μm or less. Is 3 or more. These conductive metal oxides of the present invention may be coated from a coating liquid without a binder, and a preferable coating amount is 1 g / m.
² or less, more preferably 0.001 to 0.5 g / m
² , more preferably 0.005 to 0.3 g / m ² , and most preferably 0.01 to 0.3 g / m ² . In that case, it is preferable to further apply a binder thereon.

Further, the conductive metal oxide of the present invention is more preferably coated with a binder. The binder is not particularly limited, but it is also possible to use the above-mentioned binder, for example, gelatin or dextran,
It may be a water-soluble binder such as polyacrylamide, starch or polyvinyl alcohol, or poly (meth) acrylic acid ester, polyvinyl acetate, polyurethane, polyvinyl chloride, polyvinylidene chloride, styrene / butadiene copolymer, polystyrene, polyester, Synthetic polymeric binders such as polyethylene, polyethylene oxide, polypropylene, polycarbonate, etc. may be used in the organic solvent and further these polymeric binders may be used in the form of aqueous dispersions. The coating amount of the metal oxide at that time is preferably 1 g / m ² or less, more preferably 0.0
01-0.5 g / m ² , more preferably 0.005-0.
5 g / m ^2, particularly preferably from 0.01 to 0.3 g / m ^2. The coating amount of the binder is preferably 0.001~2g / m ^2, more preferably 0.005~1g / m ^2, more preferably from 0.01 to 0.5 g / m ^2. At this time, the weight ratio of the metal oxide and the binder is 1000/1 to 1/100.
0 is preferable, and more preferably 500/1 to 1/50
0, more preferably 250/1 to 1/250.
Further, these metal oxides may be used as a mixture of spherical and fibrous ones.

Next, the ionic conductive polymer or latex preferably used in the present invention will be described. The ionic conductive polymer used is not particularly limited and may be any of anionic, cationic, betaine and nonionic, but among them, preferred is anionic,
It is cationic. More preferred are anionic sulfonic acid-based, carboxylic acid-based, and phosphoric acid-based polymers or latexes, and tertiary amine-based, quaternary ammonium-based, and phosphonium-based polymers. These conductive polymers are disclosed, for example, in JP-A-48-22017 and JP-B-46-
24159, JP-A-51-30725, JP-A-51
-129216, JP-A-55-95942, JP-B-52-25251, JP-A-51-29923, JP-B-60-48024, and anionic polymers or latexes described in JP-A-48-91165 and JP-A-48-91165. Kai 49-1
No. 21523, Japanese Patent Publication No. 49-24582, Japanese Patent Publication No. 57
-18176, 57-56059, 58-56
856, US Pat. No. 4,118,231 and the like cationic polymers or latexes can be mentioned.

These conductive polymers or latices of the present invention may be coated from a coating solution without a binder, in which case it is preferable to further coat a binder thereon. The conductive polymer or latex of the present technology may be co-coated with a binder. The content of the conductive polymer or terax of the present invention is 0.005 to 5 g / m ² , preferably 0.01 to 3
g / m ^2, more preferably from 0.02 to 1 g / m ^2.
Further, the binder is 0.005~5g / m ^2, preferably, 0.01 to 3 g / m ^2, particularly preferably 0.01 to
It is 2 g / m ² . The weight ratio of the conductive polymer or latex to the binder is 100/1 to 10/100, preferably 95/5 to 15/85, and particularly preferably 90/10 to 20/80. Specific examples of these conductive polymers or latices will be described below, but the present invention is not limited thereto.

[0077]

[Chemical 3]

[0078]

[Chemical 4]

[0079]

[Chemical 5]

Ionic surfactants are also effective,
Specific examples are JP-A-49-85826 and JP-A-49-5826.
33630, JP-A-48-87826, JP-B-49
-11567, JP-B-49-11568, JP-A-5
5-70837, US2,992,108, US3
206, 312 and the like. In the layer composed of the conductive metal oxide, polymer, or latex of the present invention, a heat-resistant agent, weather-resistant agent, inorganic particles, water-soluble resin, emulsion, etc. are matted to improve the quality of the film, as long as they do not impair the antistatic property. May be added for For example, inorganic fine particles may be added to the layer made of the metal oxide of the present invention. Examples of the inorganic fine particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like.
The fine particles preferably have an average particle diameter of 0.01 to 10 μm, more preferably 0.01 to 5 μm, and preferably 0.05 to 10 parts by weight with respect to the solid content in the coating agent, and particularly preferably 0. 1 to 5 parts.

Further, various organic or inorganic curing agents may be added to the coating agent of these conductive agents. These curing agents may be low molecular weight compounds or high molecular weight compounds, and these may be used alone or in combination. Examples of low molecular weight curing agents include, for example, "The Theory of the Photog Process" by TH James.
Raphic Process) ", 4th edition, pp. 77-88, low molecular weight curing agents are used, among which those having vinyl sulfonic acid, aziridine group, epoxy group, triazine ring are preferred, and especially JP-A Sho 53-41221
And low molecular weight compounds described in JP-A-60-225143 are preferred.

The polymer hardening agent is preferably a compound having a molecular weight of 2000 or more and having at least two groups that react with a hydrophilic colloid such as gelatin in the same molecule, and reacts with a hydrophilic colloid such as gelatin. Examples of the group include an aldehyde group, an epoxy group, an active halide (dichlorotriazine, chloromethylstyryl group, chloroethylsulfonyl group, etc.), an active vinyl group, an active ester group and the like. Examples of the polymer curing agent used in the present invention include polymers having an aldehyde group such as dialdecit starch, polyacrolein and acrolein copolymers described in US Pat. No. 3,396,029, and US Pat. No. 3,623. , 878, Polymers with Epoxy Groups, Research Disclosure 1733
3 (1978) and the like having a dichlorotriazine group, the polymer having an active ester group described in JP-A-56-66841, JP-A-5-
6-142524, U.S. Pat. No. 4,161,407.
Polymers having an active vinyl group described in, for example, JP-A-54-65033 and Research Disclosure 16725 (1978), or a group which is a precursor thereof are preferable, and JP-A-56-142524 is particularly preferable. Preference is given to active vinyl groups or groups which are the precursors thereof being linked to the polymer main chain by means of long spacers, as described.

The conductive metal oxide, polymer, latex or ionic surfactant addition layer used in the present invention is not particularly limited, and examples thereof include a protective layer, an intermediate layer, an emulsion layer,
UV layer, antihalation layer, undercoat layer, back layer,
A back protective layer can be mentioned. Of these, a protective layer, an intermediate layer, an antihalation layer, an undercoat layer, a back layer and a back protective layer are preferable, and an undercoat layer, a back layer, an intermediate layer and an antihalation layer are particularly preferable. The electric resistance of the antistatic layer produced as described above is preferably as low as possible, and is 10 ¹³ Ω or less at 25 ° C. and 60% relative humidity, preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, More preferably 10
It is less than ¹⁰ Ω. It is needless to say that this conductivity is preferably provided before the photosensitive material is developed, but it is desirable that the conductivity can be maintained even after the developing treatment. From this viewpoint, a conductive metal oxide is more preferable.

In the present invention, an anion, nonion, cation or betaine fluorine-containing surfactant can be used in combination. These fluorine-containing surfactants are disclosed in JP-A-49-1
0722, British Patent No. 1,330,356, JP-A Nos. 53-84712, 54-14224, and 50-.
113221, U.S. Pat. Nos. 4,335,201, 4,347,308, British Patent 1,417,915.
No. 52/26687 / 57-26719
No. 59-38573, JP-A-55-149938.
No. 54, No. 54-48520, No. 54-14224, No. 58-200235, No. 57-146248, No. 5
8-196544, British Patent No. 1,439,402
No., etc. Preferred examples of these are described below.

F-1 C ₈ F ₁₇ SO ₃ K F-2 C ₇ F ₁₅ COONa F-3 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) -CH ₂ COOK F-4 C ₈ F ₁₇ SO _{2 N (C 3 H 7) -} (CH 2 CH
_{(OH) CH 2 O) 3} - (CH 2) 4 SO 3 Na F-5 C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH
₂ O) ₄ (CH ₂ ) _4- SO ₃ Na F-6 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ -O
-P (= O) (ONa) 2 F-7 C 8 F 17 CH 2 CH 2 OOC-CH 2 -CH
_{(SO 3 Na) -OCOC 8 H} 17 F-8 C 8 F 17 SO 2 NHCH 2 CH 2 CH 2 (OCH
^{_{2 CH 2) -N (+)}} (CH 3) 2 -CH 2 COO (-) F-9 C 8 F 17 SO 2 NHCH 2 CH 2 N-N (+) (
^{_{CH 3) 3 · I (-}} ) F-10 C 8 F 17 SO 2 NHCH 2 CH 2 CH 2 (OCH 2 CH 2) 3 N (+) (CH 3) 3 ·
_{CH 3 -C 6 H 4 -SO 3} (-) F-11 C 8 F 17 SO 2 N (C 10 H 21) - (CH 2 CH
₂ O) ₁₆ H

Further, in the present invention, a nonionic surfactant may be used. Specific examples of the nonionic surfactant preferably used in the present invention are shown below. _{N-1 C 11 H 23 COO} (CH 2 CH 2 O) 8 H N-2 C 17 H 33 COO (CH 2 CH 2) 5 (CH 2 -CH (OH) -CH 2) 3 (CH 2 CH 2
_{O) 5 H N-3 C} 16 H 33 O (CH 2 CH 2 O) 12 H N-5 C 9 H 19 -C 6 H 4 -O (CH 2 CH 2 O) 10
H The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material. , A lubricant layer, an antistatic layer, and the like.

The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention is preferably 0.0001 to 1 g / m ² per layer, more preferably 0.01 to 1 g / m ² .
005 to 0.5 g / m ² , particularly preferably 0.0005 to
It is 0.2 g / m ² . Further, two or more kinds of these surfactants of the present invention may be mixed. Further, a polyol compound such as ethylene glycol, propylene glycol, 1,1,1-trimethylolpropane, etc., as shown in JP-A-54-89626, may be added to each layer of the present invention. Other known surfactants may be added to the photographic layer of the present invention alone or as a mixture. Although they are used as coating aids, they are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvement of photographic characteristics.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be color or black and white. 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. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having 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 a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
A coupler, a DIR compound, etc. as described in the specifications of 1-20037 and 61-20038 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 or British Patent No. 923,045, JP-A-57-1127.
No. 51, No. 62-200350, No. 62-20654.
No. 1, No. 62-206543, No. 56-25738.
No. 62-63936, 59-202464,
It is described in JP-B-55-34932 and JP-B-49-15495. The silver halide grains have regular crystal shapes such as cubes, octahedra and tetradecahedrons, irregular crystal shapes such as spheres and plates, and crystal defects such as twin planes. It may have one or a combination thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 1764.
3 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and ibid.
18716 (November 1979), p.648, Graphide, "Physics and Chemistry of Photography", published by Paul Montell (P. G.
lafkides, Chemie et Phisique Photographique, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin Photographic Emul).
sion Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., VL Zelikman et al., Making and Coating Photog
It can be prepared using the method described in raphic Emulsion, Focal Press, 1964) and the like. Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
and Engineering), Volume 14, 248-257 (19
70 years); U.S. Pat. Nos. 4,434,226 and 4,4
14,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, 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, 61-72238, 6).
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.

Couplers that release a photographically useful residue upon coupling are 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, 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 U.S. Pat. No. 4,130,427, U.S. 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 and 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 the high boiling point solvent 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 T1 /
2 is preferably 30 seconds or less. The film thickness is 25 ° C and relative humidity is 5
Means the film thickness measured under 5% humidity control (2 days), and the film swelling rate T1 / 2 can be measured according to a method known in the art. For example, A Green (A. Gree
n) Photographic Science and
Engineering (Photogr. Sci. Eng.), Volume 19, 2
No., pages 124-129, and can be measured by using a swellometer (swelling meter) of the type described above, and T1 / 2 is the maximum swelling film thickness reached when processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. 90% of the saturated film thickness is defined as the time required to reach the film thickness of T1 / 2. The film swelling rate T1 / 2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling 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, pages 28-29, and the same No.
Development can be carried out by a usual method described in the left column to the right column of 615 of 18716. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.
For example, the Schiff base type compounds described in U.S. Pat. No. First, a description will be given of the method of measuring curl and terms and the like. (1) Core set To wrap the film around the spool and add a curl. (2) Core set curl A curl in the length direction attached by the core set. The degree of curling is ANSI / ASC pH 1.29-1
Measured according to Test Method A of 985, 1 / R [m]
(R is the curl radius). (3) Absolute core set curl This is the core set curl of the photographic film before the curl is improved. (4) Controlled core set curl 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) × 1
00

[0098]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. Example 1 A sample was prepared as follows. (1) Preparation of Support After melt-extruding a PEN chip, it was made to be 3.4 in the longitudinal direction.
Double stretching was carried out 4 times in the transverse direction to prepare a biaxially stretched support having a thickness of 90 μm. The PEN support has an extrusion temperature of 3
A film was formed at 00 ° C, a longitudinal stretching temperature of 140 ° C, a lateral stretching temperature of 130 ° C, and a heat setting of 250 ° C for 6 seconds. In addition, necessary amounts of yellow, cyan, and magenta dyes were added to each support for the purpose of preventing light piping.

(2) Surface Treatment of Support Surface Both surfaces of the support PEN were subjected to a surface treatment of ultraviolet treatment, corona treatment, glow treatment or flame treatment. For the UV treatment, the method shown in the example of JP-B-45-3828 was used. For the corona treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. was used and treated at 20 m / min. At this time, the processing intensity is calculated from the current and voltage readings.
The treatment was 0.375 kV · A · min / m ² . 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. Glow treatment was performed as follows. Four rod-shaped electrodes having a diameter of 2 cm and a length of 40 cm were fixed on an insulating plate in a vacuum tank at intervals of 10 cm. At this time, the film was set to run 15 cm away from the electrodes. Further, a heating roll having a diameter of 50 cm and equipped with a temperature controller was placed immediately before the electrode, and the film was set so as to come into contact with this heating roll for 3/4 round. A biaxially stretched film having a thickness of 90 μm and a width of 30 cm was run and heated with a heating roll so that the temperature of the film surface between the heating roll and the electrode zone was 115 ° C. The film surface temperature was controlled by contacting it with a thermocouple thermometer. Next, this film was conveyed at a speed of 15 cm / sec and subjected to glow treatment. The pressure in the vacuum chamber was 0.2 Torr, and the partial pressure of H ₂ O in the atmospheric gas was 75%. Discharge frequency is 30 KHz, output 2500 W, treatment intensity is 0.5 KV.
A · min / m ² The vacuum glow discharge electrode is Japanese Patent Application No. 5-
The method described in 147864 was followed. Flame treatment was carried out using a frame processing device manufactured by Kasuga Electric Co., Ltd. The distance between the tip of the internal flame of the burner and the support was 1 cm. The volume ratio of propane gas / air is 1/17, and the treatment strength is 15 Kca.
It was 1 / m ² .

(3) Heat Treatment of Support The PEN support was wound on a roll having a diameter of 30 cm. PEN
Was heated to 160 ° C., cooled to 115 ° C., kept at that temperature for 24 hours, and then returned to room temperature. (4) Coating of emulsion-side undercoat layer An undercoat layer having the following formulation was provided on both surfaces of the surface-treated PEN support. The dry film thickness was designed to be 0.01 μm. Gelatin 1 part by weight Distilled water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene dichloride 50 parts by weight P-chlorophenol 4 parts by weight

(5) Coating of Back First Layer The back first layer was the same as the above emulsion side undercoat layer. (6) Coating of second layer of bag 230 parts by weight of stannic chloride hydrate and 23 parts of antimony trichloride
A part by weight was dissolved in 3000 parts by weight of ethanol 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 obtained precipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was centrifuged, water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation.
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 an incinerator heated to 600 ° C. to prepare a tin oxide-antimony oxide composite having an average primary particle size of 0.005 μm. A fine particle powder was obtained. The specific resistance of this fine particle powder was 1 Ω · cm. Fine particle powder 4
A 1N aqueous sodium hydroxide solution was added to a mixture of 0 parts by weight and 60 parts by weight of water to roughly disperse with a stirrer, and then dispersed with a horizontal sand mill to disperse conductive particles having an average particle diameter of secondary particles of 0.15 μm. (PH = 7.0) was obtained.

A liquid having the following formulation was applied and dried at 110 ° C. The dry film thickness was designed to be 0.2 μm. 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

(7) Coating of Back Third Layer Using diacetyl cellulose as a binder, a coating solution was prepared according to the following formulation.・ Silicon dioxide (average particle size 0.3 μm) 0.01 parts by weight ・ Aluminum oxide 0.03 parts by weight ・ Diacetyl cellulose 1.0 parts by weight ・ Methyl ethyl ketone 9.4 parts by weight ・ Cyclohexanone 9.4 parts by weight ・ Poly (polymerization 10) Oxyethylene paranonylphenol ether 0.06 part by weight-Trimethylolpropane 3 toluene diisocyanate adduct 0.03 part by weight-Colloidal silica (aerosil average particle size 0.02 μm) 0.02 part by weight-C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ CH ₂ O) ₆ H 0.01 parts by weight Poly (vinylidene difluoride / vinylidene tetrafluoride) 0.01 parts by weight (molar ratio 9: 1) Poly (methyl methacrylate) / Divinylbenzene) 0.01 parts by weight (molar ratio 9: 1, average particle size 1.0 μm) At over, dry film thickness of 1.5μm
Was applied on the second layer of the back. Drying is 11
It was performed at 5 ° C. for 3 minutes.

(8) Coating of back fourth layer The following two types of slip agents were mixed in a ratio of 4: 1, an equal weight of xylene was added, and the mixture was heated and dissolved at 100 ° C. and then stirred while applying ultrasonic waves. did. Further, 10 times the weight of the slip agent solution at room temperature isopropanol was added all at once to this solution to prepare a slip agent dispersion. This dispersion was diluted with xylene / cyclohexanone / isopropanol (70/25/5 weight ratio), and a high-pressure homogenizer (25 ° C, 300 kg / cm ² ) was used.
Was finely dispersed to obtain a lubricant coating solution having a lubricant concentration of 0.1% by weight. Application is slide coating method 15
It was carried out at a concentration of mg / m ² and dried at 115 ° C. for 5 minutes. _{n-C 17 H 35 COOC 30} H 61 -n 4 parts by weight _{n-C 30 H 61 O (} CH 2 CH 2 O) 10 H 1 part by weight (9) Preparation 5 wt% gelatin aqueous solution 200 of the matting agent of the present invention 0.1 parts by weight of stearic acid was added to parts by weight and heated to 50 ° C. Then, 200 parts by weight of a polymer solution of dichloromethane (30 wt%) was added, and the mixture was dispersed by a three-one motor for 1 hour. After 1 hour, 500 parts by weight of water was added to stop the dispersion. Further, 5000 parts by weight of water was added to the matting agent thus produced, and the matting agent was classified by a centrifuge. (10) Evaluation of number average particle diameter and particle size distribution of matting agent An electron micrograph of the matting agent was taken, and the number average particle diameter and particle size distribution of 600 matting agents were examined. (11) Coating of photosensitive layer Each layer having the composition shown below was multilayer-coated on a support having an undercoat to prepare a multilayer color photosensitive material. The matting agent of the present invention is the outermost layer of the photosensitive layer (second protective layer).
Was contained in. (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.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 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-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 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 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10-4 ExS-2 1.0 × 10-4 ExS-3 3.4 × 10-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10-5 ExS-5 2.1 X10-4 ExS-6 8.0 x10-4 ExM-2 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) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10-5 ExS-5 2.2 × 10-4 ExS-6 8.4 × 10-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10-5 ExS-5 8.1 × 10-5 ExS-6 3.2 × 10-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10-4 ExC-8 7.0 × 10-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 -3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 -4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10-2 HBS-4 5.0 × 10-2 PMMA (average particle size 0.2 μm) Table See 1 Colloidal silica (average particle size 0.01μm) See Table 1 Gelatin 1.8

Fourteenth Layer (Second Protective Layer) Silver Iodobromide Emulsion M Silver 0.10 H-1 0.40 B-1 (Developer-insoluble matting agent of the present invention) See Table 2 B-2 (Dissolution of developer of the present invention) Matting agent) See Table 2 B-3 0.05 S-1 0.20 Gelatin 0.70

[0119]

[Table 1]

[0120]

[Table 2]

Further, in order to improve storage stability, processability, pressure resistance, antifungal / bacteriostatic property, antistatic property and coating property, each layer may be provided with W-1 to W-3, B-4 to B-. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0122]

[Table 3]

In Table 1, (1) Emulsions J to L 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 I 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 the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
was μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0126]

[Chemical 6]

[0127]

[Chemical 7]

[0128]

[Chemical 8]

[0129]

[Chemical 9]

[0130]

[Chemical 10]

[0131]

[Chemical 11]

[0132]

[Chemical 12]

[0133]

[Chemical 13]

[0134]

[Chemical 14]

[0135]

[Chemical 15]

[0136]

[Chemical 16]

[0137]

[Chemical 17]

[0138]

[Chemical 18]

[0139]

[Chemical 19]

[0140]

[Chemical 20]

[0141]

[Chemical 21]

(10) Processing of sample The sample was cut into a film having a width of 35 mm and 24 sheets taken. Development of these samples was carried out as follows. (11) Development Processing of Photographic Film The obtained photographic film was developed by the following method.
The developing machine used was a cine type automatic developing machine FNCP-900 manufactured by Fuji Photo Film Co., Ltd. Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriamine pentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 g Hydroxylamine Sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5 g Water was added to 1.0 liter pH 10.0 Bleaching liquid Ethylenediaminetetraacetic acid ferric Ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water was added to 1.0 liter pH 6.0

Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 g Sodium bisulfite 4.6 g Water was added to 1.0 liter pH 6.6 Stabilizer formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water added 1.0 liter

The following items were evaluated on the sample manufactured as described above. (1) Evaluation of blocking properties of the emulsion layer and the back layer (Evaluation 1) A sample of 24 sheets having a width of 35 mm was processed for conditioning for 3 hours at 25 ° C. and 85% RH, and then a spool having a core diameter of 8 mm Wrapped around. The core diameter is smaller than the conventional core diameter (10 mm). This was placed in a sealed container and left at 40 ° C. for 1 day to evaluate the adhesiveness between the emulsion side and the back side. (Evaluation 2) Samples before development processing processed in the same manner as above
After conditioning the humidity at 5 ° C. and 60% RH for 3 hours, it was wound on a spool having a diameter of 8 mm. This was placed in a sealed container and left at 80 ° C. for 2 hours to evaluate the adhesiveness between the emulsion side and the back layer. When there was no adhesion mark on the film, it was evaluated as ◯, and when there was adhesion mark, it was evaluated as x. (2) Evaluation of Transparency of Photograph (Evaluation of Haze) The haze of the film after the development treatment was evaluated by a haze meter NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the value, the better the transparency. A haze value of less than 17 was evaluated as ◯, and a haze value of 17 or more was evaluated as x. (3) Evaluation of Graininess of Photograph The film after photography and development was magnified 16 times and visually evaluated whether the image quality was rough. When the distortion of the outline of the subject due to the matting agent on the print, pinholes, and roughness of the screen were not confirmed, it was rated as ○, and when it was confirmed, as ×.

(4) Evaluation of Adhesion Trace on Photograph The film after photography and development was magnified 16 times and visually evaluated for adhesion trace. ○ If there is no adhesive mark on the print, ○, if it is visible ×
And (5) Evaluation of curl habit The sensitive material prepared as described above was slit into a width of 35 mm and a length of 1.2 m. After humidity-controlling this at 25 ° C. and 60% RH overnight, the photosensitive layer was rolled up and wound on an 8 mm spool. This was placed in a closed container and heated at 80 ° C. for 2 hours to give a rolling habit. The light-sensitive material having a crease habit was allowed to cool in a room at 25 ° C. for 12 hours, then taken out from the closed container and developed, and immediately subjected to curl measurement using a curl plate under the conditions of 25 ° C. and 60% RH. The development processing conditions are as described above. The degree of rolling habit is ANSI / ANC pH 1.29
-Measured according to Test Method A of 1985, 1 / R
[M] (R is the radius of the curl). The smaller the value is, the less the curl is. (6) Evaluation of Folding of Film During Development Processing The film after development processing was visually observed, and those having no crease were marked with ◯, and those with creases were marked with x. (7) Evaluation of development processing unevenness The developed photosensitive material was magnified and printed 16 times, and it was examined whether there was processing unevenness due to the development processing on the screen. The case where there was no processing unevenness was marked with ◯, and the case where there was processing unevenness was marked with x.

(8) Evaluation of Adhesion (Adhesion) between Support and Photosensitive Layer, and Support and Back Layer After development, the emulsion layer and back layer of the film were cross-cut with a single-blade razor at intervals of 5 mm, with 7 lines in each length and width. After making a notch, an adhesive tape (Nitto tape manufactured by Nitto Denki Kogyo Co., Ltd.) was stuck on this, and after 5 hours, it was quickly peeled off in the direction of 180 ° to perform a peeling test. If both the emulsion layer and the back layer did not peel at all, it was judged as "good", and if either one peeled at all, it was judged as "peeled".

The evaluation results are shown in Tables 4-9. The support PEN having a glass transition temperature (Tg) of 119 ° C. is heat-treated at 115 ° C. for 24 hours, and corona treatment, ultraviolet treatment, glow treatment,
The silver halide emulsion layer is surface-treated by any method of flame treatment and has a number average grain size of 1 to 10 μm, and the number of grains present in a grain size range of ± 60% of the number average grain size is 0.1 to 1000 mg of a developing treatment solution-soluble matting agent and a developing treatment solution-insoluble matting agent each of which is 80% or more
/ M ² in the present invention the levels 1 to 28 that contains, retains the mechanical properties superior even to thinning and difficult attached curl,
It has a support for firmly adhering the silver halide emulsion layer, and it has excellent blocking properties even on a film wound on a spool with a diameter of 8 mm, which is smaller than conventional ones, and has photographic properties after development (transparency, graininess). It was possible to obtain a silver halide photographic light-sensitive material which does not deteriorate the temperature. In addition, 115 of PEN
It was found that the pre-heat treatment of the present invention at 150 ° C. before the heat treatment at 0 ° C. further improves the curl. The curl of the silver halide photographic light-sensitive material has a value of 1 / R [m] of 7
It was found that when it was 0 or less, the film did not fold or the development processing unevenness did not occur.

In the comparative example of level 29, the support was not surface-treated in PEN, so that the emulsion layer and the back layer were peeled off. In the comparative example of level 30, in which the PEN was not subjected to the heat treatment, the curl was markedly formed, so that the film was broken and the development process was uneven. Number average particle size ± 60
% Of particles present in a particle size of 80% is less than 80% B-1
In the comparative example of level 31 containing (matte agent insoluble in developer), the graininess of the photograph after development processing was poor. This was due to the large number of huge particles appearing in the particle size print due to the wide particle size distribution. In the comparative example of level 32, in which B-1 (matte agent of the present invention insoluble in developer) exceeding 1000 mg / m ² was applied, the transparency of the sensitizer and the graininess of photographs were deteriorated. This is because the excessive amount of the matting agent deteriorates the light transmittance. The number average particle size of B-1 (the matting agent of the present invention insoluble in the developing solution) is 10 μm.
In the comparative example of level 33 exceeding m, the graininess of the photograph was poor. This was due to the appearance of huge particles in the print. B-2 (developing solution-soluble matting agent of the present invention) was eliminated, and only B-1 (developing solution-insoluble matting agent of the present invention) was used. I got worse. This indicates that the blocking property and the transparency of the light-sensitive material cannot both be achieved by the developer-dissolving matting agent of the present invention alone. In the comparative example of level 35 in which the matting agent of the present invention was not used at all, the blocking property was poor.

[0150]

[Table 4]

[0151]

[Table 5]

[0152]

[Table 6]

[0153]

[Table 7]

[0154]

[Table 8]

[0155]

[Table 9]

The thickness of the PEN support is 50, 75,
Similar results were obtained at 100, 200 and 300 μm. Furthermore, when the support having Tg = 50 ° C. or higher shown in Table 10 was examined in the same manner as above, PEN
The exact same result was obtained. Therefore, the glass transition temperature (Tg) is 50 to 200 ° C. and the thickness is 50 to 300.
The support made of a polyester derivative having a thickness of
(Tg-50 ° C.) heat treatment for 0.1 to 1500 hr and surface treatment by any of corona treatment, ultraviolet treatment, glow treatment and flame treatment, and the silver halide emulsion layer has a number average grain diameter of 1 to 1 The developing treatment solution-soluble matting agent and the development treatment solution-insoluble matting agent each having a particle number of 80% or more in the range of particle diameters of 10 μm and ± 60% of the number average particle diameter are 0. By containing 1 to 1000 mg / m ^2, it retains excellent mechanical properties even when it is thinned, has less curl, has a support for firmly adhering the silver halide emulsion layer, and has a smaller diameter than before. It was shown that a silver halide photographic light-sensitive material excellent in blocking property even on a film wound on a spool of 8 mm and having no deterioration in photographic properties (transparency, graininess) after development processing can be obtained.

[0157]

[Table 10]

[0158]

The silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of the support has a glass transition temperature (Tg) of 50 ° C. to 200 ° C., a thickness of 50 to 300 μm, and a Tg of 0.1 at (Tg-50 ° C)
˜1500 hr heat treatment, and having a support surface-treated by any of corona treatment, ultraviolet treatment, glow treatment and flame treatment, and having a number average on at least one layer having a silver halide emulsion layer. Particle size is 1-10 μm
And the developing treatment solution-soluble matting agent and the developing treatment solution-insoluble matting agent having the number of particles present in the particle size range of ± 60% of the number average particle diameter of 80% or more, respectively.
The inclusion of 1 to 1000 mg / m ² does not deteriorate the photographic properties (transparency, graininess) after development processing, and blocking even when wound on a spool with a small diameter, that is, when the winding strength of the film becomes strong. It is possible to provide a silver halide photographic light-sensitive material which has excellent properties, retains excellent mechanical properties even when thinned, has less curl, and has a silver halide emulsion layer firmly adhered thereto.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 1/795 1/81 1/91

Claims (8)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of a support, wherein the support has a glass transition temperature (Tg) of 50 ° C. to 200.
0.1 to 1500 hr at Tg to (Tg-50 ° C.)
A polyester support which is heat-treated and has a thickness of 50 to 300 μm, and at least one layer on the side having a silver halide emulsion layer has a number average particle size of 1 to 10 μm and a number average particle size. 0.1 to 1000 mg / m ² of a developing treatment solution-soluble matting agent and a developing treatment solution-insoluble matting agent in which the number of particles present in a particle size range of ± 60% of the diameter is 80% or more A silver halide photographic light-sensitive material characterized by the above. 2. The fine particles according to claim 1 are acrylic acid,
A silver halide photographic light-sensitive material, which is fine particles composed of a polymer of a carboxylic acid derivative, an ester thereof, methacrylic acid, an ester thereof and a styrene. 3. The support of the silver halide photographic light-sensitive material according to claim 1 has a glass transition temperature (Tg) of 90 ° C. to 20 ° C.
A silver halide photographic light-sensitive material, which is a polyester derivative at 0 ° C. 4. A silver halide photographic light-sensitive material, wherein the support according to any one of claims 1 to 3 is preheated at a temperature of Tg or higher and lower than a melting point before being heat-treated. 5. A silver halide photographic light-sensitive material characterized in that the surface of the support according to any one of claims 1 to 4 is surface-treated by at least one of corona treatment, ultraviolet treatment, glow treatment and flame treatment. material. 6. A silver halide photographic light-sensitive material, wherein the support according to any one of claims 1 to 5 comprises a naphthalenedicarboxylic acid and a polyester derivative containing ethylene glycol as a main component. 7. A silver halide photographic light-sensitive material characterized in that the support according to any one of claims 1 to 6 is polyethylene-2,6-naphthalenedicarboxylate. 8. The development processing solution-soluble matting agent according to claim 1, which is a mixture of methyl methacrylate and methacrylic acid.
Copolymerization compound of 0/40 to 50/50 (molar ratio), or 60/40 to 5 of methyl methacrylate and acrylic acid
A silver halide photographic light-sensitive material, which is a copolymer compound of 0/50 (molar ratio).