JPH0961964A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance adhesiveness between a support and the photographic constituent layers and to restrain dimensional change before and after development processing by coating the film support composed essentially of a syndiotactic polystyrene with a coating fluid containing a solvent having a specified solubility parameter and a resin to form an undercoat layer. SOLUTION: The undercoat layer is formed on one side of the photographic film support composed essentially of the syndio-tactic polystyrene (SPC) by coating the support with the coating fluid containing the solvent having a solubility parameter (SP value) of 8.0-9.8, preferably, 8.5-9.7, embodied by cyclohexane or xylene or toluene, and the resin. The silver halide emulsion layer is formed on this undercoat layer, and resins to be used for the undercoat layer are not specified, but it is preferred to use a resin composed of at least one kind selected from acrylic, styrene, and polyester type resins as a copolymer component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a support having excellent dimensional stability against changes in humidity. When the support is used, the adhesiveness with photographic constituent layers, and further the dimensional stability before and after development processing are used. Relates to a silver halide photographic light-sensitive material excellent in

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material generally has a layer containing a hydrophilic colloid such as gelatin as a binder,
Such a hydrophilic colloid layer has a defect that it easily expands and contracts in response to changes in humidity, and has a characteristic that it contracts when the humidity is low and expands when it is high.

Further, due to this hydrophilic colloid layer,
The light-sensitive material has a characteristic that its dimensions change before and after development processing. This is a phenomenon in which the image size on the photosensitive material during exposure and the image size on the photosensitive material and the image size on the photosensitive material after development processing differ, and the temperature conditions during exposure and the drying temperature and humidity conditions during development It is caused by the influence.

This dimensional change of the light-sensitive material is a very important defect in a light-sensitive material for printing which requires reproduction of a dot image or a precise line image for multicolor printing.

Specifically, the film original plate for color printing is composed of three original plates of cyan, magenta, and yellow or four original plates including a sumi plate, and therefore dimensional stability is required as one set of original plates. Therefore, if the dimensional accuracy of the four original plates does not match exactly, it causes color misregistration. In addition, dimensional accuracy is also extremely required for maps and the like.

As a method for obtaining a light-sensitive material excellent in so-called dimensional stability with little change in dimensional accuracy, a technique of defining the thickness ratio between the hydrophilic colloid layer and the support is disclosed in US Pat. No. 3,201,250. In addition, the technique of incorporating a polymer latex in the hydrophilic colloid layer is disclosed in Japanese Patent Publication No. 39-39.
No. 4272, No. 39-17702, No. 43-1348.
No. 2, US Pat. Nos. 2,376,005 and 2,763.
No. 625, No. 2,772,166, No. 2,852,3
86, 2,853,457, 3,397,98
No. 8.

One of the main causes of the dimensional change of the photosensitive material is the dimensional change of the support itself. In order to solve this problem, in JP-A-3-131843, a so-called syndiotactic polystyrene (hereinafter also referred to as "SPS") in which the main chain of the main chain is a racemo chain is used as a photographic support. Proposed. This is a film having less dimensional change with respect to humidity as compared with a polyester film such as polyethylene terephthalate which has been widely used as a photographic support. However, since SPS has high crystallinity and its surface is hydrophobic,
It has a drawback that it is more difficult to impart adhesiveness to a photographic constituent layer by surface treatment than polyester.

Further, even when the SPS support is used, the dimensional change with respect to humidity can be solved, but the dimensional change before and after the development processing is not sufficiently resolved.

[0009]

In order to solve the above problems, an object of the present invention is to use syndiotactic polystyrene, which is dimensionally stable against changes in humidity, as a photographic support when used as a photographic support. Another object of the present invention is to provide a photographic light-sensitive material having a strong adhesiveness and an improved dimensional change before and after the development processing.

[0010]

The above object of the present invention has been attained by the following constitution.

1) A solubility parameter (SP value) of 8.0 to 9. is provided on at least one side of a photographic film support containing syndiotactic polystyrene as a main component.
No. 8 has a subbing layer coated with a coating liquid containing a solvent and a resin, and at least one silver halide emulsion layer is provided on the subbing layer. .

2) The solubility parameter of the solvent is 8.
5 to 9.7, The silver halide photographic light-sensitive material described in 1 above.

3) The silver halide photographic light-sensitive material as described in 1 or 2 above, wherein the content of the solvent is 10% by volume or more based on all the solvents in the coating solution.

4) Any one of the above items 1 to 3, wherein the resin constituting the undercoat layer contains at least one selected from acrylic, styrene and polyester as a copolymerization component. The described silver halide photographic light-sensitive material.

5) The surface tension of the surface of the support is 45d.
5. The silver halide photographic light-sensitive material as described in any one of 1 to 4 above, wherein the undercoat layer is coated after surface treatment to yne / cm or more.

That is, as a result of the examination in accordance with the object of the present invention, the dimensional change of the SPS support before and after the developing treatment is caused by the adhesiveness between the support and the photographic constituent layers, and the adhesion is further strengthened. It turned out that it can be improved by doing.

Hereinafter, the present invention will be described specifically.

-Syndiotactic polystyrene film support-In the present invention, syndiotactic polystyrene (S
The film containing PS as a main component means that the stereoregular structure (tacticity) is mainly a syndiotactic structure, that is, a carbon-carbon bond or a phenyl group or a substituted phenyl group which is a side chain with respect to the formed main chain. Are those having a steric structure alternately located in the opposite direction, the main chain of the main chain is a styrene polymer that is a racemo chain, or a composition containing it, is a styrene homopolymer, It is possible to polymerize by the method described in JP-A No. 62-117708, and other polymers can be polymerized by the method described in JP-A Nos. 1-46912 and 1-178505. Obtainable.

The tacticity is quantified by a nuclear magnetic resonance method (13C-NMR method) using isotope carbon. The tacticity measured by 13 C-NMR method is the existence ratio of a plurality of continuous structural units, for example, 2
In the case of styrene-based polymer having a syndiotactic structure, the styrene-based polymer mainly having a syndiotactic structure can be represented by a diad in the case of three, a triad in the case of three, and a pentad in the case of five. % Or more, preferably 85% or more, or racemic triad 60% or more, preferably 75% or more, or racemic pentad 30% or more, preferably 50% or more.

Specific monomers of the polymer constituting the syndiotactic polystyrene-based composition include styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, A single or a mixture containing vinyl benzoate as a main component. In particular, a copolymer of alkyl styrene and styrene has a
This is a preferable combination for obtaining a film having a thickness of at least m.

The polystyrene-based resin having a syndiotactic structure of the present invention uses the above-mentioned raw material monomers as a catalyst for polymerization and is disclosed in JP-A-5-320448, p.
(A) Transition metal compound and (b) described on page 10
Those containing aluminoxane as a main component, or (b) (a)
It can be produced by polymerization using a compound containing, as a main component, a transition metal compound and a compound capable of reacting with the transition metal compound (c) to form an ionic complex.

In order to produce the styrenic polymer used in the film of the present invention, first, the styrenic monomer is sufficiently purified and then polymerized in the presence of any of the above catalysts. At this time, the polymerization method, the polymerization conditions (polymerization temperature, polymerization time), the solvent and the like may be appropriately selected. Usually from -50
At a temperature of 200 ° C, preferably 30-100 ° C,
Polymerization is carried out for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane are used alone or in combination of two or more. It can be used in combination. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled, for example, by the temperature and the monomer concentration.

Further, to the extent that the effects of the present invention are not impaired,
It does not matter to copolymerize another monomer copolymerizable therewith.

The molecular weight of the SPS film of the present invention is not limited as long as it is formed, but the weight average molecular weight is preferably 10,000 to 3,000,000, and particularly preferably 30,000 to. It is preferably 1,500,000.

The molecular weight distribution at this time (number average molecular weight /
The weight average molecular weight) is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights. Further, the syndiotactic polystyrene-based film of the present invention contains syndiotactic polystyrene-based pellets at 120 to 180 ° C.
Dry for 1 to 24 hours under vacuum or under normal pressure in an atmosphere of inert gas such as air or nitrogen. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less, and more preferably 0.005% or less from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis. . However, these methods are not particularly limited as long as the purpose is achieved.

The SPS film of the present invention is preferably SPS alone made from styrene, but as a film further containing SPS, a styrene-based polymer having an isotactic structure in which the main chain is meso chain is added to SPS. The crystallization rate can be controlled by mixing the coalescence (IPS), and a stronger film can be obtained.

When SPS and IPS are mixed, the ratio depends on the stereoregularity of each other, but is 30: 7.
0 to 99: 1, preferably 50:50 to 98: 2.

The support may contain inorganic fine particles, an antioxidant, a UV absorber, an antistatic agent, a dye, a pigment, a dye, etc., in order to impart functionality, within a range not impeding the object of the present invention. Is possible.

A known method can be applied as a method of extruding at the time of film formation, but it is preferable to extrude with a T die, for example.
Syndiotactic polystyrene pellets 280-3
An unstretched film is produced by melting and extruding at 50 ° C. and cooling and solidifying while applying static electricity on a casting roll.

Next, this unstretched film was biaxially stretched to obtain 2
Orient the axis. As a stretching method, a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are sequentially performed, a sequential biaxial stretching method of transverse stretching / longitudinal stretching, a transverse / longitudinal / longitudinal stretching method, a longitudinal / transverse stretching method. -A longitudinal stretching method, a longitudinal-longitudinal-transverse stretching method, a simultaneous biaxial stretching method or the like can be adopted and can be appropriately selected according to various characteristics such as required mechanical strength and dimensional stability. .

Generally in continuous production, the longitudinal direction means the above-mentioned longitudinal stretching, and the width direction means the above-mentioned transverse stretching. That is, in continuous production, a sequential biaxial stretching method in which stretching is first performed in the longitudinal direction and then in the width direction is preferable, and in this case, the stretching ratio in the longitudinal and transverse directions is 2.5 to 6 times, and the longitudinal stretching temperature is , Depends on the glass transition temperature (Tg) of the polymer,
Stretching is usually performed in a temperature range of (Tg + 10) ° C. to (Tg + 50) ° C. In the case of a syndiotactic polystyrene film, it is preferably carried out at 110 to 150 ° C. The stretching temperature in the width direction is preferably slightly higher than that in the longitudinal direction and is preferably 115 to 160 ° C. Next, this stretched film is heat-treated. The heat treatment temperature in this case can be appropriately changed depending on the application. A temperature of 150 ° C. or lower is used for shrink-wrapping applications requiring a high shrinkage ratio, and a temperature of 150 to 270 ° C. is appropriately used for photographic, printing or medical applications requiring dimensional stability depending on the purpose.

Although the heat treatment time is not particularly limited, it is usually 1 hour.
About 2 to 2 minutes are adopted. It goes without saying that vertical heat relaxation, horizontal heat relaxation treatment and the like may be performed as necessary. After that, the film may be rapidly cooled and wound, but it is gradually cooled between Tg and the heat treatment temperature for 0.1 minute to 1500 hours, and wound on a large-diameter core, and further -0 between 40 ° C. and Tg. Cooling at an average cooling rate of 0.01 to −20 ° C./min is preferable because it has the effect of making it difficult for the support to be wound. Of course, the heat treatment between 40 ° C and Tg
From the winding of the support to the cutting of the production method after coating the emulsion, 0.
It is preferably carried out by placing it in a constant temperature bath for 1 minute to 1500 hours.

In addition to the above-mentioned film forming method, in order to impart various characteristics such as slipperiness and antistatic performance, an SPS support having the above-mentioned characteristics is laminated on at least one surface of the SPS support. It is also possible to produce an SPS laminated film.
The lamination method is such that the resin is melted in a laminar flow and then extruded from a die, or the molten SPS is extrusion-laminated on an SPS unstretched support or an SPS uniaxially stretched support that has been cooled and solidified. It is obtained by stretching in both the longitudinal and transverse directions or in the direction perpendicular to the uniaxial stretching direction and heat setting. SPS
The resin extrusion conditions, the stretching temperature, the stretching ratio, the heat setting temperature, and the like are slightly different depending on the combination of the SPS laminated supports, but they may be finely adjusted so as to select the optimum conditions and do not make a great change.

Needless to say, the laminate is composed of two or more layers, and may be a combination of the same kind of polymers (including a combination of the copolymers) or a different kind of polymers.

The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

The thickness of the thus obtained syndiotactic polystyrene-based stretched film varies depending on the application, but is 0.3 μm for ultra-thin capacitors, 6 μm and 12 μm for ordinary capacitors. There are various thicknesses such as 100 μm for medical and printing sensitive materials, and 250 μm for electrical insulating materials (slot liners, etc.), but the above film forming conditions are effective for those having a thickness of 0.3 to 500 μm. .

-Undercoat Layer- In the present invention, the syndiotactic polystyrene support has an undercoat layer formed by applying a coating solution containing at least a solvent having a specific solubility parameter (SP value) and a resin.

Solubility parameter of contained solvent (SP
Value) is preferably 8.0 to 9.8, more preferably 8.5 to 9.7, and further preferably 8.8 to 9.
It is 6. Solubility parameter of solvent mentioned above (SP
The value) is a value represented by the square root of the molecular cohesive energy, and is defined as Polymer Hand Book (Secon).
d Edition) Chapter IV Solubility
There is a description in Parameter Values, and that value is used. The unit is [cal / cm ³ ] ^1/2 .
For those without data, the heat of vaporization can be calculated from the boiling point (Polymer).
(It is described in Hand Book).

The solubility parameter (SP value) of the solvent is
Specific examples of the solvent having a pH of 8.0 to 9.8 include cyclohexane, xylene, toluene, ethyl acetate, isobutyl acetate, normal butyl acetate, isopropyl acetate, methyl isobutyl ketone, isopropyl acetate, carbon tetrachloride, and normal propylbenzene. , Diethyl ketone, ethylbenzene, dimethyl ether, xylene, methyl propyl ketone, tetrahydrofuran, butyraldehyde, benzene, chloroform,
Methyl cyclohexane, methyl ethyl ketone, trichloroethylene, chlorobenzene, methylacetone, methyl acetate, methylene chloride, ethylene dichloride, tetrachloroethane, tetrachloroethylene and the like can be mentioned.

In the present invention, the solvent may be contained at least in the undercoating coating solution, and preferably,
It is the case where the content of the solvent is 10% by volume or more, more preferably 25% or more, still more preferably 40% or more with respect to the total solvent in the undercoating liquid.

The resin constituting the undercoat layer is not particularly limited, but a polymer containing at least one selected from an acrylic type, a styrene type and a polyester type as a copolymerization component is more preferable.

As the acrylic component, methacrylic acid,
Unsaturated carboxylic acid such as acrylic acid or its ester, methyl methacrylate, hydroxymethyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, propyl methacrylate, isopropyl methacrylate, hexyl methacrylate, octyl methacrylate, methyl acrylate,
Examples thereof include ethyl acrylate, butyl acrylate, hydroxy acrylate, glycidyl acrylate, propyl acrylate, isopropyl acrylate, hexyl acrylate and octyl acrylate.

Examples of the styrene-based component include alkylstyrenes such as styrene and methylstyrene, halogenated (alkyl) styrenes such as chloromethylstyrene and chlorostyrene, and alkoxystyrenes.

The polyester component is a polymer obtained by a polycondensation reaction of a polybasic acid or its ester-forming derivative with a polyol or its ester-forming derivative. As the polybasic acid component of this polymer,
Examples include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid and dimer acid. You can Along with these components, unsaturated polybasic acids such as maleic acid, fumaric acid and itaconic acid and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used in a small proportion.

Further, as the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, triglycol Methylolpropane, poly (ethylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol.

The resin has a solubility parameter (SP
When the value) does not dissolve in a solvent having a value of 8.0 to 9.8, the solvent having the SP value may be mixed after being dissolved in a good dissolving solvent for each resin.

In the present invention, the surface of the syndiotactic polystyrene before applying the undercoat layer may be treated or untreated, but more preferably the surface tension of the surface is 45 dyne / cm (20). It is preferable to apply the undercoat layer after surface treatment at a temperature of (° C.) or higher.

As the surface treatment method of the support, the surface of the support is treated with a chemical (Japanese Patent Publication No. 34-11031, Japanese Examined Patent Publication No. 3).
8-22148, Japanese Patent Publication No. 40-2276, Japanese Patent Publication No. 4
1-16423, JP-B-44-5116) Chemical mechanical surface roughening treatment (JP-B-47-19068, JP-B 55-5104), corona discharge treatment (JP-B-3)
9-12838, JP-A-47-19824, JP-A-48-28067), flame treatment (JP-B-40-1)
No. 2384, JP-A No. 48-85126), UV treatment (JP-B-36-18915, JP-B-37-144).
No. 93, Japanese Patent Publication No. 43-2603, Japanese Patent Publication No. 43-260
No. 4, JP-B-52-25726) High frequency treatment (JP-B-49-10687), glow discharge (JP-B-Sho 3)
No. 7-17682), and further, active plasma treatment, laser treatment and the like. As described in JP-B-57-487, it is preferable that the contact angle between the surface of the support and water is 58 ° or less.

The subbing layer may be applied at any time after the syndiotactic polystyrene support is formed and during the film formation. If the hydrophobic polymer in the subbing can be stretched, it can be performed at any place such as before the longitudinal stretching during the film formation, between the longitudinal stretching and the lateral stretching, after the lateral stretching and before the heat treatment.

The method of applying the undercoat layer is not particularly limited, but various known methods can be applied. For example,
The roll coating method, the gravure roll coating method, the spray coating method, the air knife coating method, the bar coating method, the impregnation method, the curtain coating method and the like can be applied alone or in combination.

The subbing layer may be coated on the syndiotactic polystyrene support, and then the photographic photosensitive layer may be coated, but one layer is further added to impart various properties such as antistatic performance and slipperiness. Alternatively, two or more undercoat layers may be provided by coating.

A hardener is preferably mixed in the undercoat layer of the present invention.

Examples of such hardeners include aldehyde compounds such as formaldehyde and glutaraldehyde, and US Pat. Nos. 2,732,303 and 3,288.
775, British Patents 974,723, 1,167,
Nos. 207 and the like, compounds having a reactive halogen, diacetyl, ketone compounds such as cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3,5-triazine. , Divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, US Pat.
32,763, 3,635,718, British Patent 9
Compounds having a reactive olefin described in US Pat. Nos. 3,539,644 and 3,642.
No. 486, Japanese Patent Publication No. 49-13568, No. 53-472.
71, 56-48860, and JP-A-53-5725.
No. 7, No. 61-128240, No. 62-4275,
Vinyl sulfone compounds described in 63-53541 and 63-264572, N-hydroxymethylphthalimide, U.S. Pat. Nos. 2,732,316 and 2,58.
6,168, etc., N-methylol compounds, US Pat. No. 3,103,437, etc., isocyanate compounds, US Pat. Nos. 2,983,611, 3,107,2.
Aziridine compounds described in US Pat. No. 80, US Pat.
5,294, 2,725,295 and the like, acid derivatives, carbodiimide compounds described in US Pat. No. 3,100,704, epoxy compounds described in US Pat. No. 3,091,537, etc. Compound, US Pat. No. 3,321,31
No. 3, 3,543,292 and the like, organic hardeners such as isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and chromium alum, zirconium sulfate. , An inorganic hardener such as chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, JP-A-50-38540 is known.
Compounds having a dihydroquinoline skeleton described in JP-A Nos. 51-59625, 62-262854 and 6
2-2644044 and 63-184741 N-carbamoylpyridinium salts, JP-B-55-38
No. 655, the acylimidazoles described in JP-B No. 53-
22089, N-acyloxyimidazoles, and compounds having two or more N-acyloxyimino groups in the molecule described in JP-B-53-22089.
2-93470-containing N-sulfonyloxyimide group-containing compounds, JP-A-58-113929, phosphorus-halogen bond-containing compounds, JP-A-60-2
25148, 61-240236, 63-41.
Examples thereof include chloroformamidinium compounds described in No. 580. The addition amount of these is 1
It is preferably 0.001 to 10 g per liter.

-Silver Halide Photosensitive Layer- The halogen composition of silver halide in the silver halide emulsion used in the present invention is not particularly limited, but in the case of processing with a small replenishment amount or in the case of performing rapid processing. Is silver chloride, 60
It is preferable to use a silver halide emulsion composed of silver chlorobromide containing silver chloride in an amount of mol% or more and silver chloroiodobromide containing silver chloride in an amount of 60 mol% or more.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")).

The shape of the silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. Gives a silver halide emulsion having a substantially uniform grain size.

In order to bring out the effect of the present invention remarkably, the silver halide emulsion of at least one silver halide emulsion layer contains tabular grains, and all of the emulsion layers in which the tabular grains are used. It is preferable that 50% or more of the total projected area of the grains be tabular grains having an aspect ratio of 2 or more. Particularly, as the proportion of tabular grains increases from 60% to 70%, and more preferably to 80%, more favorable results are obtained. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

Among these tabular grains, tabular grains having a (100) plane as a main plane and having a silver chloride content of 50 mol% or more are preferably used, and these are described in US Pat. No. 5,26.
4,337, 5,314,798, 5,32
No. 0958, etc., and the desired tabular grains can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. Further, in order to control the photosensitizing nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions. The preparation of the particles can be appropriately selected from an acid method, a neutral method, an ammonia method and the like.
When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5. Ammonia, thioethers, thiourea compounds, thione compounds and the like can be used as a silver halide solvent in order to control grain growth during formation of tabular grains. As a thioether compound, 3, described in German Patent 1,147,845
6,9,15,18,21-hexoxa-12-thiatricosane; 3,9,15-trioxa-6,12-dithiaheptadecane; 1,17-dioxy-3,9-15-
Trioxa-6,12-dithiaheptadecane-4,14
-Dione; 1,20-dioxy-3,9,12,18-
Tetroxa-6,15, -dithiaeicosan-4,17
-Dione; 7,10-dioxa-4,13-dithiahexadecane-2,15-dicarboxamide. JP-A-56-
94347, oxathioether compounds described in JP-A-1-121847, JP-A-63-259653,
Examples thereof include cyclic oxathioether compounds described in JP-A No. 63-301939. Especially as thiourea,
Those described in No. 82408 are useful. Specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea; 1,3-dimethylimidazole-2-thione; 1,
3-dimethylimidazole-4-phenyl-2-thione; tetrapropylthiourea and the like.

At the time of physical aging or chemical aging, metal circles such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. Iridium 10 to obtain high illuminance characteristics
Doping in the range ^-9 to 10 ^-3 is often conventional in silver halide emulsions. In the present invention, rhodium, ruthenium, osmium and / or rhenium are preferably doped in the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide in order to obtain a high contrast emulsion.

When the metal compound is added to the particles,
Metals include halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl,
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A No. 2-20.
No. 82, No. 2-20853, No. 2-20854, No. 2-20855, and hexadentate ligands described as common alkali complex salts such as sodium salt, potassium salt, cesium salt or first, There are secondary and tertiary amine salts. Also, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these are, for example, K ₂ [RuC
l ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO)
Cl ₄ (SCN)], K ₂ [RuCl ₅ (H ₂ O)], and the like. Ru part is Rh, Os, R
e, Ir, Pd, and Pt can be used instead.

Rhodium, ruthenium, osmium and /
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion.

It is often the case that better results are obtained when a large amount is present in the shell portion. In addition, a method of increasing the existing amount may be used as it is continuously outside the particles, in addition to localizing in a discontinuous layer structure. The addition amount can be appropriately selected within the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978) or cited therein.

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499 and Japanese Patent Laid-Open No. 50-71325.
JP-A No. 60-150046 and the like can be preferably used.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion according to the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

An inorganic or organic hardener is added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention as a crosslinking agent for the hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compound (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.) ), Mucohalogen acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activating type hardener, etc., alone or in combination. Can be used. These hardeners are available from Research Disclosure.
loss) 176, 17643 (issued in December 1978), page 26, paragraphs A to C.

Examples of the polymer latex contained in the photographic light-sensitive material of the present invention include US Pat.
No. 2,166, No. 3,325,286, No. 3,41
No. 1,911, No. 3,311,912, No. 3,52
No. 5,620, Research Disclosure (Res
search Disclosure No. 195
As described in 19551 (July 1980) and the like, there are hydrates of vinyl polymers such as acrylic acid ester, methacrylic acid ester and styrene.

The polymer latex preferably used in the present invention is a homopolymer of a metaalkyl acrylate such as methyl methacrylate or ethyl methacrylate, a homopolymer of styrene, or a metaalkyl acrylate, styrene and acrylic acid, N-methylol acrylamide, Copolymers with glycidol methacrylate and the like, homopolymers of alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, or copolymers of alkyl acrylate and acrylic acid, N-methylol acrylamide and the like (preferably copolymers such as acrylic acid and the like. Polymerization component is up to 30% by weight), homopolymer of butadiene or copolymer of butadiene and one or more of styrene, butoxymethyl acrylamide, acrylic acid, vinylidene chloride-methyl chloride. Acrylate - like terpolymer acrylic acid.

It is particularly preferable that the latex which can be used in the present invention has a Tg of 20 ° C. or lower, but the Tg of a polymer latex composed of a copolymer of two or more components can be easily adjusted by changing the component ratio. .

The preferred range of the average particle size of the polymer latex used in the present invention is 0.005 to 1 μm, especially 0.02.
０．２0.2 μm.

The preferable amount of gelatin in the emulsion layer is 5.0 g.
/ M ² or less is preferable, and 3.0 g / m ² or less is particularly preferable. The amount of gelatin is shown as the measured value after conditioning the humidity for 24 hours in the environment of 23 ° C. and 55% RH.

The polymer latex used in the present invention may be contained on only one side of the support, or may be contained on both sides. When both sides of the support are contained, the type and / or amount of the polymer latex contained on each side may be the same or different.

Further, the layer to which the polymer latex is added can be added in any of the silver halide emulsion layer side and the backing layer side.

Various other additives are used in the light-sensitive material used in the present invention. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

-Processing method for silver halide photographic light-sensitive material-The silver halide photographic light-sensitive material according to the present invention is an automatic processor having at least four processes of developing, fixing, washing (or stabilizing bath) and drying after exposure. Is preferably photographically processed.

As the developing solution used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc., aminophenols (for example, o-aminophenol, p-aminophenol, N)
-Methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA iron) Salt, DTPA nickel salt, etc.) may be used alone or in combination. Among them,
It is preferable to use a developing solution containing ascorbic acid and its derivatives. Ascorbic acid and its derivatives are
Known as a developing agent, for example, US Pat.
8548, 2688549, 3022168, 3
512981, 4975354 and 532681
Those described in the specification of No. 6 and the like can be used.

In the present invention, the developing agents for ascorbic acid and its derivatives and 3-pyrazolidones (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) and dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone monosulfonate, hydroquinone monosulfonic acid sodium salt, 2,5-hydroquinone) It is more preferable to use a developing agent such as potassium disulfonic acid salt) in combination. When used in combination, the developing agent of 3-pyrazolidones, aminophenols or dihydroxybenzenes substituted with a hydrophilic group is usually used in an amount of 0.01 or more and less than 0.2 mol per liter of the developing solution. Is preferred. In particular, a combination of ascorbic acid and its derivative with 3-pyrazolidones, and a combination of ascorbic acid and its derivative with 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

In the present invention, the developer contains an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine). Etc.) are preferably added. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol or more and 1.5 mol or less.
It is in the range of mol or less. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole,
Benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or alkali metal salts thereof, nitrilotriacetate salts, polyphosphate salts etc.), development accelerators (eg US Pat. No. 2,304, No. 025, Japanese Patent Publication No. 47-45541, etc.), a hardener (eg glutaraldehyde or its bisulfite adduct), or an antifoaming agent can be added. The pH of the developer is 7.5 or more 1
It is preferably adjusted to less than 0.5. More preferably, the pH is 8.5 or more and 10.4 or less.

As the fixing solution, those having a generally used composition can be used. Fixers generally have a pH of 3
~ 8. As a fixing agent, sodium thiosulfate, potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixing solution contains a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates having a water softening ability. Compounds such as agents may be included.

In the present invention, the ammonium ion concentration in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution.

The ammonium ion concentration is particularly preferably in the range of 0 to 0.05 mol per liter of the fixing solution. As the fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

In the present invention, the concentration of acetate ion in the fixing solution is preferably less than 0.33 mol / liter. The type of the acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates the acetate ion in the fixing solution. However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used, and particularly sodium salt. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably 0.22 mol or less per liter of the fixing solution,
Particularly preferably, the amount is 0.13 mol or less, whereby the acetic acid gas generation amount can be highly reduced. Most preferably, it is substantially free of acetate ions.

The fixer contains citric acid, tartaric acid, malic acid,
Salts such as succinic acid and optical isomers thereof are included. As salts of citric acid, tartaric acid, malic acid, succinic acid, etc., these lithium salts, potassium salts, sodium salts, ammonium salts, etc., such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, potassium potassium tartaric acid, tartaric acid Sodium potassium and the like may be used. Of these, more preferred are citric acid, isocitric acid, malic acid, succinic acid and salts thereof. Most preferably, malic acid and its salt.

After fixing treatment, washing and / or stabilizing bath is used. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Used in combination with polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc.), aldehydes (eg formalin, glyoxal, glutaraldehyde etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts) , Polyphosphates, etc., antifungal agents (for example, phenol, 4-chlorophenol, cresol, o-phenylphenol, chlorophene, dichlorophene, formaldehyde, p-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzo. Imidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-
Trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
Specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole,
Mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.).
Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

In order to reduce the amount of waste liquid, the present invention is processed while fixing and replenishing a fixed amount proportional to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per m ² . Preferably 30 to 25 per 1 m ² respectively
0 ml.

In order to reduce the amount of waste liquid, the development replenishment amount is 1
It is preferably 250 ml or less per m ² , and more preferably 30 to ²⁰⁰ ml per 1 m ² . The fixing replenishment amount and the development replenishment amount here indicate the amounts to be replenished. Specifically, it is the replenishing amount of each liquid when replenishing the same liquid as the developing mother liquid and the fixing mother liquid, and each concentrating liquid when replenishing with the liquid obtained by diluting the developing concentrated liquid and the fixing concentrated liquid with water. And the total amount of water,
It is the total amount of each solid processing agent volume and water volume when the solid development processing agent and solid fixing processing agent are replenished with a liquid dissolved in water. It is the total volume of each solid processing agent volume and water volume when replenished separately. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as or different from the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

According to the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 60 when the processing is performed by using the automatic developing machine in order to shorten the developing time. It is preferably not more than 10 seconds and not more than 10 seconds. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing, stabilization, and drying. This is a time including all the time of the process, that is, a time of Dry to Dry. Total processing time is 1
If the time is less than 0 second, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dr)
y) is 15 to 50 seconds. Further, in order to stably process a large amount of photosensitive material of 100 m ² or more, the developing time is preferably 18 seconds or less and 2 seconds or more.

In order to bring out the effect of the present invention remarkably, a heat transfer member having a temperature of 60 ° C. or higher (for example, 60 ° C.) is used in an automatic processor.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Heat energy of copper, stainless steel,
Those which transmit infrared rays by transmitting heat to a radiator such as nickel or various ceramics) and have a zone for drying are preferably used.

As the heat transfer material having a temperature of 60 ° C. or higher,
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller, and the gear is rotated in the carrying direction by the drive means and the drive transmission means. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

Further, the temperature controller is connected to a thermistor arranged in contact with the outer peripheral surface of the heat roller, and the temperature controller detects the temperature from the thermistor at 60 ° C to 150 ° C, preferably 70 ° C to 130 ° C. Therefore, it is preferable to control the halogen heater on and off.

The following examples can be given as examples of the radiant body emitting a radiant temperature of 150 ° C. or higher. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer material having a temperature of 60 ° C. or higher and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

Further, in the present invention, an automatic developing machine having the method and mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regeneration purifying agent and apparatus: JP-A-6-250352, page (3), page "0011" to page (8), page "0058".

(3) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(4) Rinse bath between developing bath and fixing bath: JP-A-4-313749, page (18), "0054" to (2)
1) Page "0065".

(5) Water replenishment method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(6) Method for controlling the drying air of the automatic developing machine by detecting the outside air temperature and humidity: JP-A-1-315745 49
6 (2) lower right column to 501 (7) lower right column and JP-A-2-108051, 588 (2) lower left column to 589
(3) The lower left column of the page.

(7) Silver recovery method for fixing waste liquid: JP-A-6-
No. 27623, page (4) “0012” to page (7) “00”
71 ".

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EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1-Polymerization of syndiotactic polystyrene (SPS) -SPS pellets were prepared according to JP-A-3-131843. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. In a glass container having an internal volume of 500 ml, 17.8 g of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) (7
(1 mmol) 200 ml of purified benzene and 24 ml of trimethylaluminum were added, and the mixture was stirred at 40 ° C. for 8 hours to adjust the catalyst. This was placed under an argon gas flow. After filtering through 3 glass filters, the filtrate was freeze-dried. This was taken out, put in a 2 l stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein, and heated to 90 ° C.

1 l of purified styrene was put in this,
Further, add 70 ml of purified p-methylstyrene,
The polymerization reaction was continued at this temperature for 8 hours. Thereafter, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added to the catalyst to deactivate the catalyst while further stirring. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried. The weight average molecular weight of this polymer was 415,000, which was obtained from the results of GPC measurement using standard polystyrene at 135 ° C. using 1,2,4-trichlorobenzene as a solvent.

The melting point of this polymer is 13 at 245 ° C.
It was confirmed from the C-NMR measurement that the polymer obtained had a syndiotactic structure. This was pelletized with an extruder and then dried at 130 ° C.

-Preparation of Syndiotactic Polystyrene Film (SPS) Support-The pellets obtained by the above polymerization example were melt extruded at 330 ° C. in an extruder. This molten polymer was extruded through a pipe into an extrusion die. Then, the SPS unstretched sheet having a film thickness of 1000 μm was obtained by extruding while being electrostatically applied to the cooled casting drum through the die slit and cooling.

The prepared sheet was preheated at 115 ° C. and then stretched 3.3 times in the machine direction. It was preheated at 100 ° C in a tenter and then stretched 3.3 times in the transverse direction at 130 ° C. While slightly relaxing in the lateral direction, heat set at 225 ° C to 100
A SPS film support 1 having a thickness of μm was obtained.

-Coating of Undercoat Layer- Sample 1 was prepared by coating an undercoating coating solution <U-1> having the following composition on both surfaces of the obtained SPS film support 1 so that the dry film thickness was 1 μm. The support was created.

<U-1> (Resin A) Acrylic resin (I) 20 g Composition: Butyl acrylate 40 wt% Styrene 40 wt% 2-Hydroxyethyl acrylate 20 wt% Solvent I: Cyclohexane 750 cc Solvent II: Acetone 250 cc Undercoat An undercoating coating solution was prepared in the same manner except that (solvent I) in the coating solution <U-1> was changed from cyclohexane to the solvent shown in Table 1 to give a dry film thickness of 1 μm on both surfaces of the SPS film support 1. Thus, the supports of Samples 2 to 14 were prepared.

Furthermore, 18 W / (m ² · mi is provided on both sides.
After corona discharge of n), the following coating solution A-1 was applied to the emulsion layer coating side so that the dry film thickness was 0.1 μm, and the following coating solution B-1 was applied to the back layer coating side. Was applied to give a dry film thickness of 0.8 μm.

<Coating Liquid A-1> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 1g Finish with water 1000ml

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<Coating Liquid B-1> Gelatin 10 g Inorganic metal oxide SnO ₂ / Sb (9/1 weight ratio) 10 g Average particle size 0.25 μm Sodium dodecylbenzenesulfonate 0.3 g Dihexyl-α-sulfone succinate sodium Salt 1.2 g Finish with water 1000 ml-Coating of emulsion layer and back layer-The following <emulsion layer> and <backing layer> are coated on the support of the obtained samples 1 to 14 to prepare a silver halide photographic light-sensitive material. It was created.

(Preparation of emulsion) A silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 parts of a rhodium chloride complex.
A solution added so as to have a concentration of × 10 ^-5 mol / Agmol was simultaneously added to a gelatin solution while controlling the flow rate, and after desalting, a cubic crystal having a particle size of 0.13 µ and containing 1 mol% of silver bromide,
A monodispersed silver chlorobromide emulsion was obtained.

This emulsion was sulfur-sensitized by a conventional method to obtain 6-methyl-4-hydroxy-1,3,3a, stabilizer as a stabilizer.
After adding 7 tetrazaindene, the following additives were added to prepare an emulsion coating solution.

(Preparation of Emulsion Coating Solution) Gelatin 1.0 g / m ² Compound (a) 1 mg / m ² NaOH (0.5 N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² saponin (20%) 0.5 cc / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e)
10 mg / m ² compound (f) 6 mg / m ² latex (m) 1.0 g / m ² styrene-maleic acid copolymerized aqueous polymer (thickener) 90 mg / m ² .

(Emulsion Protective Layer Coating Solution) Gelatin 0.5 g / m ² compound (g) (1%) 25 cc / m ² compound (h) 120 mg / m ² spherical monodisperse silica (8 μ) 20 mg / m ² 〃 ( 3 μ) 10 mg / m ² compound (i) 100 mg / m ² latex (m) 0.5 g / m ² citric acid pH adjusted to 6.0.

(Backing Layer Coating Liquid) Gelatin 1.0 g / m ² compound (j) 100 mg / m ² compound (k) 18 mg / m ² compound (l) 100 mg / m ² saponin (20%) 0.6 cc / m ² Latex (m) 300 mg / m ² 5-Nitroindazole 20 mg / m ² Styrene-maleic acid copolymer aqueous polymer (thickener) 45 mg / m ² Glyoxal 4 mg / m ² .

(Backing Protective Layer Coating Liquid) Gelatin 0.5 g / m ² Compound (g) (1%) ² cc / m ² Spherical polymethylmethacrylate (4 μ)
25 mg / m ² sodium chloride 70 mg / m ² glyoxal 22 mg / m ² compound (n) 10 mg / m ²

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The photosensitive materials 1 to 14 prepared as described above were evaluated as described below, and the results are shown in Table 1.

<Evaluation Method><< Adhesiveness of Photosensitive Material >> The adhesion of a sample to a film in a dry state before development was evaluated by the following evaluation methods.

The sample before the development treatment was carried out at 23 ° C. and 55% RH.
After leaving it for 24 hours at 40 ° C., it was scratched with a razor at an angle of 45 ° from the surface to the support, a cellophane tape was pressure-bonded, and it was rapidly peeled off, and the peeled area of the emulsion layer was evaluated on a scale of 5.

Evaluation Criteria A: Very strong adhesion and no peeling B: Strong adhesion, peeling area less than 5% C: Strong adhesion, peeling area 5% or more, less than 20% D: Peeling area Is 20% or more and less than 50% E: Peeling area is 50% or more and less than 100% F: Completely peeling Incidentally, the evaluation C or more has a practical adhesive force.

<< Evaluation Method of Dimensional Difference Before and After Treatment >> The obtained sample was cut into a size of 30 cm × 60 cm, and two fine lines were separated at a distance of about 56 cm using a bright room printer P-627FM (manufactured by Dainippon Screen Co., Ltd.). Was subjected to image exposure and developed to obtain a document. This original, unexposed sample (the same size as the original), printer and automatic processor at 23 ° C, 20% R
After conditioning the humidity for 12 hours in H, an unexposed sample was contact-exposed (face-to-face) to the original and processed by an automatic developing machine. The humidity of the developed sample was adjusted for 12 hours, then the sample was overlaid on the original document, and the distance between the fine lines was measured with a loupe with a scale. The measurement was performed at n = 6, and the average was taken. [Dimensional difference (a) before and after treatment] The same experiment was performed at 23 ° C. and 60% RH to obtain 20% R
The difference with the value of the dimensional difference before and after the treatment under H (the dependency on the environmental humidity is shown) was taken. [(B) value] When the (a) value exceeds ± 20μ, the dimensional deviation is conscious, and when the (b) value exceeds 20μ, it is conscious that the dimensional difference before and after the treatment is changed, and some working condition is set. This is the level that needs to be changed.

(Standard Processing Conditions) Process Temperature Time Liquid Immersion Time Development 28 ° C. 30 seconds 26 seconds Fixing 28 ° C. 26 seconds 22 seconds Washing 18 ° C. 18 seconds 18 seconds Drying 45 ° C. 14 seconds Total 66 seconds Each step time is the next step Including the so-called wading transport time up to and including the soaking time does not include the wading transport time. [Developer formulation] (Composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount for adjusting pH of working solution to 10.6 Potassium bromide 4.5 g (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 mg Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid ( 90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer is used, the above composition A and composition B are dissolved in 500 ml of water in this order to make 1 l. Used.

[Fixing Solution Formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / V aqueous solution) 8.1 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 5.8 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1) % W / V aqueous solution) 26.5 g When the fixing solution was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was made up to 1 liter. The pH of this fixer was about 4.3.

[0137]

[Table 1]

As is clear from the results shown in Table 1, the samples of the present invention have a strong adhesiveness with the photographic constituent layers and have improved dimensional change before and after the development processing.

Example 2 In preparing the undercoating coating solution <U-3> of Example 1,
An undercoated support was prepared in the same manner except that the type and amount of (solvent I) and (solvent II) were prepared as shown in Table 2, and the support was used as in Example 1. Samples 15 to 24 were prepared by coating the same silver halide emulsion layer and back layer. The obtained sample was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0140]

[Table 2]

As is clear from the results shown in Table 2, the samples of the present invention have a strong adhesiveness with the photographic constituent layers and have improved dimensional change before and after the development processing.

Example 3 In the preparation of the undercoating coating solution <U-3>, except that the resin A was the following resins B to L and the solvent I was toluene, the undercoating coating solution shown in Table 3 was prepared. Was used to prepare an undercoated support in the same manner as in Example 1, and the support was used in Example 1
Samples 25 to 35 were prepared by coating a silver halide emulsion layer and a back layer similar to the above. The obtained sample was evaluated in the same manner as in Example 1, and the results are shown in Table 3.

(Resin B) Acrylic resin (II): Methyl acrylate (Resin C) Acrylic resin (III): Ethyl acrylate (Resin D) Acrylic resin (IV): Methyl methacrylate 90% by weight Acrylic acid 10% by weight (Resin E) Acrylic resin (V): 90% by weight of ethyl methacrylate Itaconic acid 10% by weight (Resin F) Styrene resin (I): Styrene (Resin G) Styrene resin (II): Styrene 50% by weight Butadiene 50 % By weight (Resin H) Polyester resin (I): Dimethyl terephthalate 25% by weight Dimethyl adipate 25% by weight Ethylene glycol 50% by weight (Resin I) Polyurethane resin: Polyurethane (Resin J) Cellulose resin (I): Nitro Cellulose (Resin K) Cellulose resin (II): Diacetylcellulose Scan (resin L) polycarbonate resin: Polycarbonate

[0144]

[Table 3]

As is clear from the results shown in Table 3, the samples of the present invention have a strong adhesiveness with the photographic constituent layers and have improved dimensional change before and after the development process.

[0146]

According to the present invention, when the syndiotactic polystyrene, which is dimensionally stable against humidity change, is used as a photographic support, the adhesiveness with the photographic constituent layers is strengthened and the dimensional change before and after the development process is suppressed. Can provide an improved silver halide photographic light-sensitive material.

Claims (5)

[Claims] 1. A coating liquid containing a solvent having a solubility parameter (SP value) of 8.0 to 9.8 and a resin on at least one side of a photographic film support containing syndiotactic polystyrene as a main component. Having an undercoat layer coated with,
A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on the undercoat layer. 2. The solubility parameter of the solvent is 8.5 to
2. The silver halide photographic light-sensitive material according to claim 1, which is 9.7. 3. The solvent is 1 for all the solvents in the coating liquid.
The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the content is 0% by volume or more. 4. The resin constituting the undercoat layer contains at least one selected from an acrylic type, a styrene type and a polyester type as a copolymerization component. A silver halide photographic light-sensitive material as described in the above item. 5. The surface tension of the surface of the support is 45 dyn.
The silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein the undercoat layer is coated after surface treatment to e / cm or more.