JPH02195340A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material superior in dimensional stability during processing by incorporating a specified compound in a hydrophilic colloid, applying and drying it in specified conditions and storing it in an atmosphere having <=1% absolute humidity. CONSTITUTION:At least one hydrophilic colloidal layer formed on a polyester substrate contains one of the compounds represented by formula I in which R is H or optionally substituted alkyl, such aralkyl, or such aryl, and n is 0 or 1. The colloidal layer containing water in an amount of <=300% of the dry basis of the binder is dried under a relative humidity of <=50%, and then stored under an absolute humidity of <=1%, thus permitting dimensional variation due to the development processing to be perfectly prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a silver halide photographic material with improved film physical properties, and particularly to a silver halide photographic material with excellent dimensional stability.

(Problems with the Prior Art) Silver halide photographic materials generally include a layer containing a hydrophilic colloid such as gelatin as a binder on at least one side of a support. Such a hydrophilic colloid layer has the disadvantage that it easily expands and contracts due to changes in humidity and temperature.

Dimensional changes in photographic materials due to expansion and contraction of the hydrophilic colloid layer are extremely serious drawbacks in photographic materials for printing, which require the reproduction of halftone images and precise line drawings for multicolor printing. becomes.

Dimensional stability with little dimensional change
A technique for specifying the thickness ratio of a hydrophilic colloid layer and a support in order to obtain a photographic material with excellent stability is disclosed in U.S. Pat. No. 39-4272, No. 39-17702, No. 43
-13482, No. 45-5331, U.S. Patent No. 23
No. 7600, No. 2763625, No. 2772166, No. 2852386, No. 2853457, No. 339
No. 7988, No. 3411911, and No. 3411912. In addition, the theoretical support for the above technology is
er) by Photographic Science and
Engineering (Photo, Sc1. and Etr.
(1957) pp. 69-73.

However, in the printing field where multicolor printing and precise reproduction of line drawings are required, further improvement in dimensional stability is strongly desired. Although dimensional stability is particularly important before and after processing steps (developing, fixing, washing, drying) that photographic films necessarily undergo, techniques that incorporate polymer latex do not provide sufficient improvement.

This is because the support stretches due to water absorption during the treatment process, but even after the subsequent drying process, the base elongation does not return to its original state for a long period of time, and elongation remains in practice.

Therefore, when comparing the dimensions of an untreated film and a treated film, the latter is often in an elongated state.

In the art, this phenomenon is expressed as poor dimensional stability due to processing, and this is a particularly serious drawback in photographic materials for printing.

In order to improve the dimensional stability accompanying this development process, Japanese Patent Application No. 62-94133 discloses a technique using a vinylidene chloride undercoat layer.

However, even if this technique is used, it is not possible to completely improve the dimensional stability associated with development processing, and further improvements have been desired.

(Problems to be Solved by the Present Invention) A first object of the present invention is to provide a silver halide photographic material that has excellent dimensional stability during processing.

A second object of the present invention is to provide a silver halide photographic material that has excellent dimensional stability in response to environmental changes.

(Means for solving the interpolation point) These objects of the present invention are 1) in a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a polymer latex on at least one side of a polyester support; On the polyester support, a compound represented by the following formula (]) is contained in at least one hydrophilic colloid layer, and when coating and drying,
The moisture of 300% or less based on the dry weight of the binder contained in all the layers formed on the support is dried at a relative humidity of 50% or less, and the silver halide photographic light-sensitive material is dried at an absolute humidity of 1% or less. A silver halide photographic material characterized by being stored under an atmosphere.

General formula (I) where R is a hydrogen atom, an alkyl group, an aralkyl group,
It represents an aryl group, and these groups may be substituted.

n represents O or l.

2) The halogenation of 1) above, in which the support is made of a polyester coated on both sides with three or more polymer layers having a thickness of 0° and made of a copolymer containing 70 to 99.5% by weight of vinylidene chloride. This was achieved using silver photographic materials.

Various ideas have been made to improve the dimensional stability associated with development processing, but a significant improvement has been made by controlling the humidity during coating and drying of silver halide photographic materials and the subsequent storage humidity. This was something that could not have been predicted.

The silver halide photographic material of the present invention must be stored at an absolute stability of 1% or less after being dried at a relative humidity of 50% or less with a moisture content of 300% or less based on the dry weight of the binder. .

At this time, in ordinary silver halide photographic materials, the reaction rate of the curing agent for crosslinking the binder is significantly reduced, so the swelling ratio of the hydrophilic colloid layer does not reach the desired level, and it dries during automatic processing. Inconveniences such as defects, poor passability, and insufficient film strength of the hydrophilic colloid layer may result in scratches during the development process, or in some cases, important images may be scraped off or partially lost. occurs.

Even if a fixing solution containing a hardening agent is used to solve these problems, the problem cannot be solved by using the amount of the hardening agent in an amount comparable to that used in a normal dura fixing solution. Although drying properties can be improved by using a large amount of a hardening agent, the problem arises that the hardening agent precipitates, contaminating the photographic material after processing.

Such disadvantages can be overcome by using the compound represented by the monocatalytic formula (1) of the present invention.

(Specific Structure of the Invention) -m During production of the silver halide photographic light-sensitive material, a hydrophilic colloid layer is applied as a water-soluble coating liquid onto a polyester support, and then dried.

In the present invention, when drying the hydrophilic colloid I coating solution after coating, it is necessary to dry it under conditions of a relative humidity of 300% or less and a relative humidity of 50% or less based on the dry weight of the binder.

The hydrophilic colloid layer coating solution is based on the binder dry weight.
If the moisture content exceeds 0.00%, in the present invention, the moisture content is reduced to 50% after the point where the moisture content reaches 1300% in the latter half of drying.
It is necessary to dry at a relative humidity of:

When two or more hydrophilic colloid layers are applied and dried simultaneously, the moisture content is the sum of the moisture in all layers, and the binder dry weight is the sum of the binder dry weight in all layers.

Relative humidity in the present invention is the ratio of the amount of water vapor contained in a given volume to the amount of saturated water vapor in the air, expressed as a percentage.

In the present invention, the temperature for drying the moisture of 300% or less based on the dry weight of the binder is usually preferably in the range of 25°C to 50°C.

In the present invention, drying refers to reducing the water content to such an extent that the surface of the photosensitive material does not have tackiness, preferably 15% or less, particularly 10% or less based on the dry weight of the binder. It means to reduce the water content.

In the present invention, the silver halide photographic material must be stored at an absolute humidity of 1% or less. Absolute humidity is defined as the ratio of the weight of water vapor in the air to the weight of air. For example, 1% absolute humidity is 50% absolute humidity at 25'C.
%, which corresponds to a relative humidity of about 21% at 40°C.

In order to reduce the absolute humidity to 1% or less, for example, a method is used in which a silver halide photographic light-sensitive material that has been left in this temperature and humidity atmosphere for a sufficient period of time is sealed and packaged with a moisture-proof packaging material. Another method is to reduce the moisture content of the core and paper that are packaged with the silver halide photographic material in advance, and then reduce the absolute humidity of the air inside the package to 1% or less after the package is sealed. can.

In addition, after sufficiently reducing the drying air humidity in the latter half of coating drying and reducing the atmospheric humidity in the processing area after winding,
Hermetically sealed packaging using moisture-proof packaging material is also effective. Furthermore, it is also effective to hermetically package a desiccant such as silica gel together with the silver halide photographic material.

The package for hermetically packaging the silver halide photographic light-sensitive material of the present invention may have any birch shape as long as it can seal the silver halide photographic light-sensitive material. A variety of packaging shapes can be considered depending on the shape; usually, packaging bags made by heat sealing are preferably used. The material that makes up the packaging bag is a polyethylene film with low moisture permeability (usually polyethylene containing carbon black etc. to provide light shielding properties and
It is preferable to use polyethylene containing a substance that does not adversely affect the photosensitive material in order to provide slippage on the surface.

Another preferred embodiment is a packaging bag layered with an aluminum thin film.

Preferred embodiments of these packaging bags are disclosed in Japanese Patent Application Laid-open No. 57-
No. 6754, JP-A-58-132555, JP-A-61
Examples include color materials disclosed in Japanese Patent No. -189936 and the like.

When the silver halide photographic material of the present invention is packaged in these packaging bags, it may be packaged under reduced pressure to reduce the air inside the packaging bag.In any case, in the present invention, the photosensitive material Preferably, the material is packaged and stored in a sealed form in an atmosphere of less than 1% absolute humidity.

The compound represented by the general formula (R) used in the present invention will be explained.

General formula (R), where R is a hydrogen atom, an alkyl group, an aralkyl group,
It represents an aryl group, which groups may be substituted, and n represents 0 or l.

To explain in more detail, R is a hydrogen atom or has 1 to 2 carbon atoms.
0 alkyl groups (e.g. methyl group, ethyl group, etc.), aralkyl groups having 6 to 20 carbon atoms (e.g. benzyl group, phenethyl group, etc.), aryl groups having 5 to 20 carbon atoms (e.g. phenyl group, naphthyl group, pyridyl group) etc.), and these groups may be substituted. Examples of the substituent include a sulfonic acid group, a hydroxyl group, a carboxyl group, and the like.

Particularly preferred as R is a hydrogen atom.

n represents O or l.

Specific examples of the compound represented by the general formula (1) of the present invention are listed below, but the present invention is not limited thereto.

1-1) C11[5OxCHtSOtCH-CH! ■−
4) CHx-CIISOtCIISOtCll-Cllyoz
lls l-5) CII*”'CItSOtCHSO□C1l -CIl
iCI+□ l-8) CH1 Tomi CH30□CHSO*CIi -CC11x-
The amount of the compound represented by formula (1) to be added is desirably selected depending on the type of compound example, the type of gelatin, etc., and is 0.5XIO-'' per 100g gelatin.
~50XIO-” moles are suitable, preferably 2X1
0-20×10-” moles.

03Na OO11 The compound represented by the formula (1) used in the present invention is contained in at least one of hydrophilic colloid layers such as a silver halide emulsion layer, a bank layer, a protective layer, and an intermediate layer.

For halogenated emulsions and/or other photographic constituent layers, a compound represented by the -In formula may be used in combination with a gelatin hardening agent commonly used in the art. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, diacetyl,
Ketone compounds such as cyclopentanedione, bis(2
-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,S-) riazine, and others U.S. Pat.
, No. 288, 775, No. 2. 732.303, British Patent No. 974,723, British Patent No. 1. 167.201
Compounds having reactive halogens such as those shown in No. 3, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-) riazine, and others, US Pat. , No. 3,232
．． No. 763, No. 3,490,911, No. 3,64
Compounds with reactive olefins, such as those shown in British Patent No. 2°486 and British Patent No. 994,869;
-Hydroxymethylphthalimide, other U.S. Patent No. 2
．． 732.316 and 2,586.168, isocyanates as shown in U.S. Patent No. 3.103.437, Patent No. 3.01? , No. 280, No. 2,
Aziridine compounds such as those shown in U.S. Pat. No. 983.611, U.S. Pat.
Acid derivatives such as those shown in No. 725.295, etc.
Carbodiimide compounds such as those shown in U.S. Patent No. 3,100,704, U.S. Patent No. 3,091
, U.S. Pat. No. 3.321.313, U.S. Pat. No. 3.543, U.S. Pat.
Inoxazole compounds such as those shown in No. 292, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium aerobane and zirconium sulfate. There is.

The hydrophilic colloid layers of the photographic light-sensitive material of the present invention include a silver halide emulsion layer, a bank layer, a protective layer, an intermediate layer, etc., and wood-philic colloids are used in these layers. Gelatin is most preferable as the woody colloid, and examples of the gelatin include so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivatives, modified gelatin, etc.
Any gelatin commonly used in the art can be used, but lime-treated gelatin and acid-treated gelatin are preferably used.

In addition to gelatin, proteins such as colloidal albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; $I derivatives such as agar, sodium alginate, and starch derivatives; binary hydrophilic colloids such as polyvinyl alcohol and poly- N-vinylpyrrolidone polyacrylic acid copolymer, polyacrylamide, derivatives thereof, partial hydrolysates, etc. can be used. Mixtures of two or more of these colloids can be used if desired.

The polymer latex used in the present invention has an average particle size of 2
An aqueous dispersion of a water-insoluble polymer of 0 mμ to 200 mμ,
The preferred amount used is 0.01 to 1.0, particularly preferably 0.01 to 1.0, in terms of dry explosion weight ratio, to 1.0 of the gelatin used as the binder. It is 1 to 0.8.

Preferred examples of the polymer latex used in the present invention include alkyl esters, hydroxyalkyl esters, or glycidyl esters of acrylic acid, or alkyl esters, hydroxyalkyl esters, or glycidyl esters of methacrylic acid as monomer units, and have an average molecular weight of 100,000 or more, particularly preferably 3
It is a polymer of 00,000 to 500,000, and a specific example is shown by the following formula.

Polymer 1 + C11z-CI + -C00
C#lII Polymer 2 Polymer 3 Polymer 4 Polymer 5 Polymer 6 COOC! H5-G-C11! -CI! +1 0OCJs C)13 −+ CH2−C+.

0OCJt H 0OII Furthermore, regarding polymer latex,
5-533L U.S. Patent No. 2,852,386, 3062
The descriptions in the specifications of No. 674, No. 3411911, and No. 3411912 can be referred to.

The polymer latex used in the present invention is contained in at least one of wood-philic colloid layers such as a silver halide emulsion layer, a bank layer, a protective layer, and an intermediate layer.

The present invention is particularly effective in ultra-high contrast window materials containing hydrazine derivatives.

Regarding ultra-high contrast sensitive materials containing such hydrazine derivatives and image forming methods using the same, US Pat. No. 4,224,4
No. 01, No. 4,168.977, No. 4,166.7
No. 42, 4.241. No. 164, No. 4.272,
No. 606, JP-A No. 60-83028, JP-A No. 60-218
No. 642, No. 60-258537, No. 61-2237
It is described in No. 38, etc.

The hydrazine derivative used in the present invention is preferably one represented by the following general formula (Q).

-Formula (Q) Q-1) Y In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl group, or an arylsulfonyl group, an alkyl or arylsulfinyl group, represents a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfaniyl group, or a heterocyclic group; It represents a substituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

Representative compounds among the compounds represented by -ta formula (Q) are shown below.

Q-2) Q-3) C! H.

N Q-5) Q-7) Furthermore, the present invention also provides a method for obtaining high contrast by processing a photosensitive material containing a tetrazolium compound with a PQ type or MQ type developer containing a relatively high concentration of sulfite. This effect can be achieved. Image forming methods using tetrazolium compounds are described in JP-A-52-18317, JP-A-53-17719, and JP-A-53-17720.

The silver halide emulsion of the photographic window light material used in the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing it below.

As the silver halide, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used, and there are no particular limitations on the grain form and size distribution.

The silver halide emulsion layer can contain photosensitive silver halide, chemical sensitizers, spectral sensitizers, antifoggants, film physical property improvers such as surfactants, thickeners, and the like. Regarding these, see Research Disclosure, 176
The description in Vol. 17643 (December 1978), and JP-A No. 52-108130, No. 52-114328, No. 52-121321, No. 53-3217, No. 53-
The description in the specification of No. 44025 can be referred to.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent Publication No. 58-9412.

The surface protective layer is a layer with a thickness of 0.3 to 3 μm, particularly 0.5 to 1.5 μm, containing a hydrophilic colloid such as gelatin as a binder, and contains a capping agent such as fine particles of polymethyl methacrylate, It contains colloidal silica and, if necessary, a thickener such as potassium polystyrene sulfonate, a gelatin hardening agent, a surfactant, a slip agent, a UV absorber, and the like.

The back layer is a layer using a hydrophilic colloid such as gelatin as a binder, is non-photosensitive, and may have a single layer structure or a multilayer structure including an intermediate layer, a protective layer, etc.

The thickness of the back layer is 0.1μ to lOμ, and if necessary, it contains a gelatin hardener, a surfactant, a capping agent, a colloidal silica, a slip agent, and a UV ray as well as a silver halide emulsion layer and a surface protective layer. It may contain absorbents, dyes, thickeners, etc.

The method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer, but typically photographic materials using a halogen compound as a photosensitive component, such as photosensitive materials for printing and photosensitive materials for X-ray. The effects of the present invention are particularly remarkable in photosensitive materials for printing.

There are no particular limitations on the exposure method, development method, etc. of the photosensitive material of the present invention;
Reference may be made to the detailed descriptions of No. 52-114328, No. 52-121321, etc., and the descriptions in the above-mentioned Research Disclosure magazine. Also, JP-A-60-
As described in US Pat. No. 2,585,37 and US Pat. No. 4,269,929, it is also possible to increase the development speed and shorten the development time by adding amines.

The vinylidene chloride copolymer in the present invention is 70 to 9
Copolymer containing 9.5% by weight, preferably 85-99% by weight of vinylidene chloride, JP-A-51-135526
A copolymer of vinylidene chloride/acrylic acid ester/vinyl monomer having an alcohol in the side chain described in No. 2, a copolymer of vinylidene chloride/alkyl acrylate/acrylic acid described in U.S. Pat. Examples include a copolymer of vinylidene chloride/acrylonitrile/itaconic acid described in US Pat. No. 2,698.235, a copolymer of vinylidene chloride/alkyl acrylate/itaconic acid described in US Pat. It will be done. Specific examples of compounds include the following.

All numbers in parentheses represent weight ratios.

Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (83:12:5) Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (83:101) Vinylidene chloride: hydroxydiethyl methacrylate) (
92:8) copolymer vinylidene chloride; methyl methacrylate:acrylonitrile (90:8+2) copolymer vinylidene chloride:
Butyl acrylate: acrylic acid (94: 4: 2
) copolymer of vinylidene chloride:butyl acrylate:itaconic acid (7
5: 20: 5) copolymer Vinylidene chloride dimethyl acrylate: itaconic acid (90: 8: 2) copolymer Vinylidene chloride: methyl acrylate dimethacrylic acid (93: 4 + 3) Vinylidene chloride-monoethyl itaconate Esther (96
:4) copolymer of vinylidene chloride:acrylonitrile:acrylic acid (96
:3. copolymer of vinylidene chloride: methyl acrylate: acrylic acid (9)
0:5:5) copolymer vinylidene chloride; ethyl acrylate: acrylic acid (9
2:5:3) copolymer vinylidene chloride:methyl acrylate:3-chloro-2
-Hydroxypropyl acrylate (84:9:
7) Copolymer of vinylidene chloride: methyl acrylate; copolymer of N-ethanol acrylamide (85:10:5) The method of coating a polyester support with the vinylidene chloride copolymer in the present invention involves coating these polymers on a polyester support. A solution dissolved in a suitable organic solvent or an aqueous dispersion can be applied by known coating methods such as dip coating, air knife coating, curtain coating, roller coating, wire barcoding, gravure coating,
Alternatively, it can be applied by an extrusion coating method using a hombar described in US Pat. No. 2,681,294. There is also a so-called extrusion coating method in which a molten polymer is made into a film and is made to flow down onto a moving polyester, which is simultaneously cooled and laminated under pressure.

In order to further improve the adhesive strength between the polyester support and the above polymer layer, the surface of the polyester support is subjected to chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, and activation. plasma treatment,
High pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment,
There is no problem with treatment such as ozone oxidation treatment.

Further, in order to firmly adhere the polymer layer used in the present invention to the polyester base, US Pat. No. 3,245,
No. 937, No. 3,143,421, No. 3,501,3
No. 01, same 3. 271. 178, polyester swelling agents such as phenol, resorcin, 0-cresol, m-cresol, trichloroacid, dichloroacetic acid, monochloroacetic acid, and chloranopebenzyl alcohol can be added. It becomes necessary. As these swelling agents, resorcinol is preferably used, but resorcinol has the drawback of often inducing spot failures during the manufacturing process.

A particularly preferred method for avoiding this technical drawback is to apply the polymer layer used in the present invention after subjecting the surface of the polyester support to a glow discharge treatment.

The glow discharge treatment in the present invention refers to any conventionally known method, for example, Japanese Patent Publication No. 35-7578, No. 3
No. 6-10336, No. 45-22004, No. 45-2
No. 2005, No. 45-24040, No. 46-4348
No. 0, U.S. Patent No. 3゜057.792, U.S. Patent No. 3.057,
No. 795, No. 3.179.482, No. 3.288.6
No. 38, No. 3,309.299, No. 3,424.73
No. 5, No. 3,462.335, No. 3.475.307
No. 3,761,299, British Patent No. 997.093
No., JP-A-53-129262, etc. can be used.

The appropriate pressure during glow discharge is o, oos to 20 Torr, preferably 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may even destroy the object to be treated. Discharge is generated by applying a high voltage between one or more pairs of metal plates or metal rods spaced apart from each other in a vacuum tank. This voltage can take various values depending on the composition and pressure of the atmospheric gas, but normally in the above pressure range it is 500~
A particularly suitable voltage range for improving adhesion is a voltage range of 2,000 to 500 volts.
~4000V.

Furthermore, as seen in the prior art, the discharge frequency ranges from DC to several 100,100 O, preferably from 50 Hz to 20 M.
Hz is appropriate. Regarding the discharge treatment strength, 0.0 IKV-A・min/lr since the desired adhesive performance can be obtained.
r ~5KV-A, min/rd.

Preferably 0.05KV-A, min/rd-IKV・A・
minutes/rd is appropriate.

The thickness of the vinylidene chloride copolymer layer in the present invention is preferably thick in order to suppress the elongation of the base due to water absorption during the development process. However, if it is too thick, it may be disadvantageous for the adhesion with the silver halide emulsion layer. arise.

Therefore, the thickness used is in the range of 0.3μ to 5μ, preferably 0.5μ to 2.0μ.

In the present invention, polyester refers to polyester whose main components are aromatic dibasic acid and glycol. Typical dibasic acids include terephthalic acid, isophthalic acid, p-
β-oxyethoxybenzoic acid, diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, etc. Glycols include ethylene glycol, propylene glycol, pukundiol, neopentylene gelylcol, 1゜4-cyclohexanediol, 1,4-cyclohexane dimetatool, 1.4-bisoxyethoxybenzene, bisphenol, diethylene glycol, polyethylene glycol, etc. There is.

Among polyesters made of these components, polyethylene terephthalate is advantageous from the viewpoint of easy availability.

There is no particular vI limit for the thickness of polyester, but it is approximately 12
A material of about μ to 200 μ, preferably about 40 μ to 180 μ is advantageous in terms of ease of handling and versatility. In particular, biaxially stretched crystallized materials are advantageous in terms of stability, strength, and the like.

In order to improve the adhesive strength between the polymer layer and the emulsion layer, a layer having adhesive properties to both may be provided as an undercoat layer. In order to further improve the adhesion, the surface of the polymer layer may be subjected to conventional pretreatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

The present invention will be further explained with reference to Examples below.

(Comparative Example) Among the undercoat supports disclosed in Example 1 of JP-A No. 60-26944, the following halogens were applied to one side of the support using the second undercoat composition 1 from the support side. A silver oxide emulsion layer and a protective layer 1 were coated and dried under the conditions shown in Table 1. Next, a bank layer and a protective layer 2 were applied to the opposite side and dried under the conditions shown in Table 1.

(1) Silver halide emulsion layer formulation In a gelatin aqueous solution kept at 50°C, 2 sulfur per mole
In the presence of X l O-' moles of rhodium chloride, a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to form silver chlorobromide monodisperse with an average particle size of 0.2μ. The emulsion was prepared. (C.I.
Composition: 95 mol 9/6) This emulsion was desalted by the flocculation method, and 1 mg of thiourea dioxide and 0.6 mg of chloroauric acid were added per 111 mol.
It was aged at ℃ until maximum performance was achieved, resulting in fog.

The following compounds were further added to the emulsion thus obtained.

n-c+tLs 2X10-S mole/Ag1 mole 1 X 10-' mole/Ag1 mole 4X10-' mole/Ag1 mole KBr 20 mg/n
(Polystyrene sulfonate sodium salt 40mg/r
d 2.6-dichloro-φ-hydroxyl 1. 3. 5-
Triazine sodium salt 30 mg/rrr This coating solution was applied so that the coating line ff was 13.5 g/m.

(2) Protected Ni prescription gelatin 1.5g/rsSin
g Fine particles (average particle size 4μ) 50mg/bododecylbenzenesulfone sulfone sodium salt 50mg/r
rr (3) Bank layer prescription gelatin 5 g/rrr Sθ, K 0J 5-nitroimidazole 15 mg/r+? 11
3-divinylsulfonyl-2 propyl 50mg/n
(N-perfluorooctanesulfonyl-N-probylglycine botadium salt 2 mB/m+ Polymer 2 (average particle size 0.06 μ) 300 mg/n in SOI (So, K so, K SO3M 5 (hK80
mg/rrr 1.3-'; Vinylsulfonyl-2propertool 150
mg/m Polymer 2 (average particle size 0.06 μ) 900 mg/rd Dihexyl alpha sulfosacnate sodium salt 10 mg/
n (Dodecylbenzenesulfonic acid sodium salt 35mg/resistant (4) Protective layer 2 prescription gelatin 0.8g/m polymethyl methacrylate fine particles (average particle size 3μ)
20mg/rrr dihexyl alpha sulfosacnate sodium salt 10mg/n (dodecylbenzenesulfonic acid sodium salt 10mg/n
l Sodium acetate 40mg/n? 99
Invention product 8 disclosed in Example-1 of No. 36 was used.

After leaving the sample sealed in a moisture-proof bag in an atmosphere at 25°C for two weeks, the following methods were used to measure (1) dimensional changes due to processing, (
2) Wet film strength and (3) drying properties by automatic processor processing were evaluated.

(1) Method for evaluating dimensional changes due to treatment Two holes with a diameter of 8 mm were drilled in the sample at 2,000 mm intervals, and after leaving it in a room at 25°C and 30% RH,
The distance between the two holes was accurately measured using a bottle gauge with m precision. The length at this time is assumed to be X11. Then, after developing, fixing, washing with water, and drying using an automatic developing machine, the dimension after 5 minutes is defined as Ym. In the industry, it is considered that there is no practical problem if the dimensional change rate (%) due to processing is 0.01% or less.

The development process was carried out using Fuji Photo Film Co., Ltd.'s FC-660 automatic processor, and the developer and fixer were manufactured by the company's GR (2).Wet film strength evaluation method.Wet film strength samples were immersed in distilled water at 25°C for 5 minutes. After that, a steel ball with a radius of 0.4 ms is attached to the sample membrane surface with a needle attached to the tip, and the load on the needle is continuously changed while moving at a speed of low/second, so that the membrane is destroyed (i.e., the sample The load (g) at which scratches were generated on the membrane surface was measured.

(3) Evaluation method of drying property by automatic development processing Size 50
．． When 10 sheets of 8×61- film were continuously processed in an environment of 30° C. and 80% R)I, it was determined how many sheets became undried.

The dry state was determined by touching the surface of the film with your hand and determining the humidity.

The absolute temperature inside the moisture-proof bag of this sample was also measured.

The relative humidity was measured under a temperature condition of 25° C., and the absolute humidity was determined using an psychrometric chart.

To measure relative humidity, use a thermohygrometer MODEL HN-T.

) 1 Dragon M [-↑EMP RECODER (Made by Senoga)
(Measure the relative humidity using sensor HN-L20 (manufactured by Chino@), and from this result, use the psychrometric diagram to determine the absolute humidity 1.
; Converted.

(Example-1) Samples (101) to (109) were prepared in the same manner as in the comparative example except that the silver halide emulsion layer formulation, protective layer 1 formulation, and back layer formulation of the hardening agent were changed as shown in Table 2. made.

Table 2 Similar to the comparative example, (1) dimensional changes due to treatment, (2
) Wet film reinforcement and (3) drying properties by automatic processor processing were evaluated.

(Example 2) A sample (
201) to (211) were prepared and similar evaluations were conducted.

(1) Silver halide emulsion layer formulation Emulsion A was prepared by the following method using the following solutions 1, 2, and 2.

1 solution; water 300+d, gelatin 9g solution 2; AgNOs 100 g, water 400-m solution; N
aCj! 37g, (NH4)3rshihcffi.

0.66■, water 400sd kept at 40°C! Solution (■) and solution (■) were simultaneously added to the solution at a constant rate. After removing the soluble salt R-t from this emulsion by a conventional method well known in the art, gelatin was added and 6-methyl-4-hydroxy-1,3,3a,7
-titraazaindene and 4-hydroxy-5,6-)
Rimethylene-1,3°3a,7-thitraazaindene was added.

This emulsion was a monodispersed emulsion with an average grain size of 0.15 μm, and the amount of gelatin contained per kg of yield of the emulsion was 60 g.

The following compounds were added to the emulsion thus obtained.

OJa polystyrene sulfonic acid, sodium salt 10mg/rr
r Compound Example 1-1) 3+㎢m g/m Polymer 2 (average particle size 0.06 μ) 500 mg/m NO.

The coating solution thus obtained was coated at a coating silver f)t3g/rrl of 0.3mg/rd.

(2) Protective layer 1 prescription gelatin 1.5g/rr? Polymethyl methacrylate fine particles (average particle size 3μ)
50mg/r+7 polymer 2 (average particle size O.

Colloidal silicariboic acid (3) Back layer prescription gelatin 06μ) 200mg/n? 350mg/Bo13mg/rrl 2g/SO-resistant Na Dodecylbenzenesulfonic acid sodium salt 25mg/i Dihexyl alpha sulfosacnate sodium salt 1Qmg/
m N-perfluorooctanesulfonyl N-bropylglycine potassium salt 2 rn g/m polystyrene sulfonic acid sodium salt 3 mg/i SO, OJ 03K SO, 180 mg/n? Sod 5OsK dihexyl alpha sulfosacnate sodium salt 2 Qmg/m Sodium dodecylbenzenesulfonate 30 mg
/a? Polystyrene sulfonic acid sodium salt 30 mg/n? Compound example + 1) 3'), S
mg/rd Polymer 2 (average particle size 0.06 μ) 200 mg/n1 (4) Protective layer 2 prescription gelatin 1 g/n? Polymethyl methacrylate imitation particles (average particle size 3/J)
40 mg/m dihexyl silefosacnate sodium salt 10 m B/rrl Dodecylbenzenesulfonic acid sodium salt 30 mg/polystyrene sulfonate sodium salt 25 mg/n (sodium acetate 30 mg/resistant (Example-3) Other than using the following support Sample (
301) to (310) were prepared and similar evaluations were conducted.

The results are shown in Table 4.

One semicircular rod electrode with a length of 40 cm and a cross section of 3 cm in diameter was used.
Four insulating plates were fixed at 0 cm intervals. This electrode plate was fixed in a vacuum tank, and a biaxially stretched polyethylene terephthalate film of 30 cm in thickness of 100 μm was run at a speed of 20 m/min on a rod 15 cm away from the electrode surface and directly facing the electrode surface. At the place where the film passes over the electrodes,
The heating roll was placed so that the film was in contact with a heating roll having a diameter of 50 cm and equipped with a temperature controller set at 120° C. for 3/4 of the circumference. Glow discharge brings the inside of the tank to 0. I
This was carried out by applying a voltage of 2000 V to the electrodes while maintaining the voltage at Torr. At this time, the electrode current is 0.5A
Met. At this time, the PET support is 0.125KVA
This means that they have been processed for 1/2 hours. In this way, both surfaces of the glow discharge treated polyethylene terephthalate were coated with an aqueous dispersion of vinylidene chloride/methyl acrylate/acrylic acid-90:5:5% by weight copolymer as a first undercoat layer to a thickness of 0.5 μm. Apply it so that it becomes 12
It was dried at a temperature of 0°C.

Furthermore, on top of that, apply the following coating solution as a second undercoat layer.
/A, and dried at a temperature of 160°C.

(1) Undercoat second layer prescription Gelatin 1.0 parts by weight Epichlorohydrin reaction product of polyamide consisting of diethylenetriamine and adipic acid 0.07 parts by weight Saponin
Add 0.01 parts by weight of water
100 parts by weight (Example-4) Example-3 except that the following silver halide emulsion layer formulation was used.
Samples (401) to (410) were prepared in the same manner as above, and the same evaluation was performed. At this time, the following developer formulation was used as the developer. The results are shown in Table-5.

(1) Silver halide emulsion layer formulation A silver chlorobromide emulsion (Br 1 mol%, average grain size 0.2μ) containing 1×10-' mol of rhodium per mol of Ag was used as a stabilizer without chemical ripening. -6-Methyl-1,3,3a,7-chitrazaindene was added. A tetrazolium salt was added to this emulsion in an amount of 5XlO-' moles per mole of Ag.

Further, as a polymer latex, Polymer 1 was added to the emulsion at a concentration of 1.4 g/ryf. As the gelatin hardening agent, the same compound as in Example-1 was used.

This emulsion was coated on birch with a coated silver amount s of 9 g/rrf and a gelatin amount of 3.1 g/rd.

(2) Developer formulation ethylenediaminetetraacetic acid disodium salt (dihydrate)
0.75g anhydrous potassium Visite
51.7g anhydrous potassium carbonate
60.4g Hydroquinone 1
5. tgl-phenyl-3-pyrazolidone 0.51 g Sodium bromide 2.2 g 5-methylbenztriazole 0, 124 g 1-phenyl-5-mercaptotetrazole 0.018
g 5-nitro-indazole 0.106g diethylene glycol 98g Add water and ti
(pH-10,5) Example-5 Sample 50 was prepared in exactly the same manner as Sample 101 except that a layer with the following composition was provided as the second undercoat layer of Sample 101 of Example-1.
1 was created.

Sample 501 showed good results similar to sample 101.

Claims (1)

[Scope of Claims] 1) In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a polymer latex on at least one side of a polyester support, a compound of the following general formula (I ) is contained in at least one hydrophilic colloid layer, and when coating and drying, the water content is 300% or less based on the dry weight of the binder contained in all layers formed on the support by 50%. 1. A silver halide photographic material, which is dried at a relative humidity of 1% or less, and stored in an atmosphere with an absolute humidity of 1% or less. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R is a hydrogen atom, an alkyl group, an aralkyl group,
represents an aryl group, which group may be substituted; n represents 0 or 1; 2) Claim 1, wherein the support is a polyester coated on both sides with a polymer layer having a thickness of 0.3μ or more and made of a copolymer containing 70 to 99.5% by weight of vinylidene chloride. The silver halide photographic material described above.