JPH01229240A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the dimensional stability of the sensitive material due to the development processing and the surrounding change of the sensitive material by incorporating a specified compd. in a hydrophilic colloid layer, and by specifying humidity at the time of applying and drying and preserving the sensitive material respectively. CONSTITUTION:The sensitive material is mounted with the hydrophilic colloid layer contg. a polymer latex on at least one side of the surfaces of a supporting body composed of a polyester, and the compd. shown by formula I is incorporated in one or more layers of the colloid layers. And, at the time of drying the coating solution of the colloid layer after applying it, less than 300wt.% of a moisture content on the dry basis of the amount of a binder contd. in the whole of the colloid layers is dried in a relative humidity of <=50%, and the obtd. sensitive material is preserved in an atmosphere of <=1% of absolute humidity. In the formula, R<1>-R<4> are each 1-20C alkyl or 6-20C aralkyl group, etc., X is a releasable group, Y<-> is an anion. The component shown by the formula is composed of a compd. shown by formula II, etc. In this case, the both surfaces of the supporting body are preferably coated with a layer composed of a copolymer contg. 70-99.5wt.% of vinylidene chloride.

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) The silver halide photographic material comprises -i, a layer containing a hydrophilic colloid such as gelatin as a binder on at least one side of the 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 important in photographic materials for printing, which require the reproduction of halftone images and precise line drawings for multicolor printing. It becomes a drawback.

Dimensional stability with little dimensional change
In order to obtain a photographic light-sensitive material with excellent stability, a technique for regulating the thickness ratio between a hydrophilic colloid layer and a support is disclosed in US Pat. -4272 No. 39-17702, No. 43-
13482, 45-5331, U.S. Patent No. 23760
No. 0, No. 2763625, No. 2772166, No. 2
No. 852386, No. 28534-57, No. 339'7
No. 988, No. 3411911, and No. 3411912. The theoretical support for the above technology is provided by J.Q.
Photographic Science and Engineering (Photo, Sci, and
Eng.) (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 elongation of the haze does not return to its original state until a long period of time has elapsed, 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 Problems) These objects of the present invention are as follows: 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 represented by the following general formula (I) is contained in at least one hydrophilic colloid layer on a polyester support, and upon 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. Silver halide photographic light-sensitive material characterized by storage under atmosphere General formula (1) % formula % RI, R2, R'' and R4 are alkyl groups having 1 to 20 carbon atoms, aralkyl groups having 6 to 20 carbon atoms , or carbon number 5
~20 aryl groups, which may be the same or different. Furthermore, R1, R2, R3, and R4 may have a substituent, or any two may combine to form a ring. X represents a group capable of leaving when the compound represented by the general formula (I) reacts with a nucleophile. YO represents an anion.

or 2) Halogenation of the above 1), in which the support is made of 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. 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 is required to have a moisture content of 300% or less based on the dry weight of the binder, and to be stored at an absolute humidity of 1% or less after being dried at a relative humidity of 50% or less.

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 rate of the hydrophilic colloid layer does not reach the desired level, resulting in poor drying during automatic processing. Or, there may be problems such as poor permeability, or even insufficient film strength of the hydrophilic colloid layer, which may cause scratches during the development process, or in some cases, important images may be scratched off or partially lost. arise.

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 general formula (1) of the present invention.

(Specific Structure of the Invention) Generally, during production of a 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 layer coating solution after coating, it is necessary to dry the coating solution at 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 00%, in the present invention, the moisture content is reduced to 50% after the point where the moisture content reaches 300% 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% relative humidity at 25°C.
At 90°C, this corresponds to a relative humidity of about 21%.

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 shape as long as it can seal the silver halide photographic light-sensitive material. Various packaging shapes are possible depending on the shape. Generally, packaging bags made by P1 Seal are preferably used. The material that makes up the packaging bag is a polyethylene film with low moisture permeability (usually polyethylene containing carbon blank etc. to provide light shielding properties and
Preferably, the material is made of polyethylene containing a substance that does not adversely affect the photosensitive material in order to provide slippage on the surface.

Another preferable form is a packaging bag in which Aluminum 1 and a thin film are layered.

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
-1.89936 etc. are mentioned.

When the silver halide photographic material of the present invention is packaged in these packaging bags, the packaging may be carried out under reduced pressure to reduce the amount of air inside the packaging bag. In any case, in the present invention, the photosensitive material is preferably stored in a sealed package in an atmosphere with an absolute humidity of 1% or less.

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

General formula (1) % Formula % R1, RE, R3 and R' are alkyl groups having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, butyl group, 2-ethylhexyl group, dodecyl group, etc.), 6 to 6 carbon atoms 20 aralkyl groups (e.g. benzyl group, phenethyl group, 3-
pyridylmethyl group, etc.), or an aryl group having 5 to 20 carbon atoms (eg, phenyl group, naphthyl group, pyridyl group, etc.), and they may be the same or different.

Further, R', R", R" and R4 may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. group, N,N-disubstituted carbamoyl group, and the like.

It is also preferred that any two of RI, R2, R3 and R4 combine to form a ring.

For example, examples of R1 and RZ or R3 and R4 bonding together to form a ring with a nitrogen atom include a pyrrolidine ring, a piperazine ring, a perhydroazepine ring, a morpholine ring, and the like.

Further, examples of R1 and R'' or R2 and R4 bonding together to form a ring with two nitrogen atoms and a carbon atom sandwiched between them include an imidacilline ring, a tetrahydropyrimidine ring, a tetrahydrodiazepine ring, etc. There are cases where it is formed.

X represents a group capable of leaving when the compound represented by the general formula (1) reacts with a nucleophile, and preferable examples include a halogen atom, a sulfonyloxy group, and a 1-pyridinyramyl group.

YO rains anions, halide ions, sulfonate ions, sulfate ions, cI! o, e, BF
40, PF6o, etc. are preferred. When YO generates a sulfonate ion, it may combine with X, R', R2, R3 or R4 to form an inner salt.

Specific examples of the compound represented by the general formula (I) of the present invention are listed below.

■-1) cu3CH.

I ■-2) CI2゜ ■-3) C2 ■-4) I ■-5) ■-6) ■-7) ■-8) ■-9) I-10) CIl, CH.

l-11) l-12) I-14) A l-16) l-17) CHi C11i 0SO□CF3 C113 The amount of the compound represented by the general formula (1) depends on the type of compound example, the type of gelatin, etc. It is desirable to select the optimum amount by
-'~50X10-3 mol is suitable, preferably 2
X10-' to 20X10-' moles.

The compound represented by the general 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 hack layer, a protective layer, and an intermediate layer.

In the silver halide emulsion layer and/or other photographic constituent layers, a compound represented by formula (1) and a gelatin hardening agent commonly used in the art may be used in combination. Examples of such curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclobentanedione, and bis(2-
(chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-) riazine, and other U.S. Pat.
288,775, British Patent No. 2,732,303, British Patent No. 974,723, British Patent No. 1,167.207, etc., compounds having reactive halogens, divinylsulfone, 5-acetyl -1,3-diacryloylhexahydro-1,3,5-triazine, etc. U.S. Patent Nos. 3.635.718 and 3.232,76
No. 3, No. 3,490,911, No. 3. 642°486, compounds with reactive olefins such as those shown in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent Nos. 2 and 7.
N-methylol compounds such as those shown in U.S. Pat. No. 32,316 and U.S. Pat. No. 2,586.168;
Isocyaners such as those shown in No. 103.437 etc.
Class 1, U.S. Patent No. 3,017,280, U.S. Patent No. 2,9
Aziridine compounds such as those shown in U.S. Pat. No. 83.611, U.S. Pat.
25.295, carbodiimide compounds as shown in U.S. Pat. No. 3,100,704, U.S. Pat. No. 3,091,
Epoxy compounds such as those shown in No. 537,
U.S. Patent No. 3,321.313, U.S. Patent No. 3,543,2
Isoxazole compounds such as those shown in No. 92, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium light pan 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 hydrophilic colloids are used in these layers. Gelatin is most preferred as the hydrophilic 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; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N-vinyl Pyrrolidone 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 0.1 to 0.8, in dry weight ratio to 1.0 of gelatin used as a binder.

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 -(-CIl□-CH-)-.

0OCJq Polymer 2 -(-CI(, -CH→-7C00Cz
Hs Polymer 3 CI+.

-(-C1, -C+.

sound C00C3H.

Polymer 4 CT.

■ Polymer 5 CT.

■ -(-CH2-CH-)-1-÷cut-c+nCOO
C4Hq C00Ctl□CHCH3I H Polymer 6 +CH, -C1 (-I, -÷C1h-CH÷.

COOCJs C00t+ Furthermore, regarding polymer latex,
5-5331, U.S. Pat. No. 2,852,386, 306
The descriptions in the specifications of No. 2674, No. 3411911, and No. 3411912 can be referred to.

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

The present invention is particularly effective in ultra-high contrast sensitive 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, same 4. 241. No. 164, No. 4,272
, No. 606, JP-A-60-83028, JP-A No. 60-21
No. 8642, No. 60-258537, No. 61-223
It is described in No. 738, etc.

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

General formula (Q) A-N-N-B Y In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, or a carbamoyl group. group, alkoxy or aryoxycarbonyl group, sulfinamoyl group, alkoxysulfonyl group, thioacyl group, thiocarbamoyl group, sulfaniyl group, or heterocyclic group, and XSY is both a hydrogen atom or one is a hydrogen atom and the other is substituted. or represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

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

Q-1) Q-2) Q-3) OCN Q-5) Q-6) Q-7) Furthermore, the present invention provides a method for converting a photosensitive material containing a tetrazolium compound into a PQ containing a relatively high concentration of sulfite. This effect can also be achieved in a method of obtaining high contrast by processing with a type or MQ type developer. 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 light-sensitive 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.

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 may contain photosensitive silver halide, chemical sensitizers, spectral sensitizers, antifoggants, film physical property improvers such as surfactants, thickeners, etc. I can do it. Regarding these, see Research Disclosure, Vol. 176, Section 17643 (December 1978).
month) and JP-A-52-108130, JP-A-52-108130.
-114328, 52-121321, 513
Reference may be made to the descriptions in No. 217 and Specification No. 53-44025.

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 contains a hydrophilic colloid such as gelatin as a binder and has a thickness of 0.3 to 3 μm, particularly 0.3 μm. 5 to 1.5 μm layer, in which a matting agent such as fine particles of polymethyl methacrylate, colloidal silica, and optionally a thickening agent such as potassium polystyrene sulfonate, a gelatin hardening agent, a surfactant, Contains a slip agent, UV absorber, etc.

The bank layer is a layer containing a hydrophilic colloid such as gelatin, 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 10μ, and if necessary, gelatin hardeners, surfactants, capping agents, colloidal silica, slip agents, UVvi absorbers, dyes, and thickeners as well as the silver halide emulsion layer and surface protective layer are included. etc. can be contained.

The method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer, but typically photographic materials using silver halide as a photosensitive component, such as photosensitive materials for printing and photosensitive materials for X-ray. , general negative light-sensitive materials, general reversal light-sensitive materials, general-purpose positive light-sensitive materials, direct positive light-sensitive materials, and the like. 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;
No. 52-114328, No. 51-121321, etc., and the descriptions in the above-mentioned Research Disclosure magazine can be referred to. Also, JP-A-60-2
As described in US Pat. No. 58,537 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: hydro; toethyl acrylate (83:12:5) Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (83:10:8) Vinylidene chloride: hydroxydiethyl methacrylate )(
Copolymer of vinylidene chloride: methyl methacrylate: acrylonitrile (90:8:2) Copolymer of vinylidene chloride: butyl acrylate: acrylic acid (94:4:2) Copolymer of vinylidene chloride: butyl Acrylate: Itaconic acid (7
5:20:5) copolymer of vinylidene chloride:methyl acrylate:itaconic acid (9
0:8:2) copolymer vinylidene chloride: medyl acrylate-1.dimethacrylic acid (93:4:3) vinylidene chloride: monoethyl itaconate (96
: , i) copolymer vinylidene chloride: acryloni-1-lyl: acrylic acid (9
6:3.5:1.5) copolymer 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 diN-ethanol acrylamide (85:10:5) As a method for coating a polyester support with the vinylidene chloride copolymer in the present invention, these polymers can be coated 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 the extrusion coating method using a hopper 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 activated plasma. process,
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, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, foamy chloral, and hensyl 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 such drawbacks is to apply the polymer layer used in the present invention after subjecting the surface of the polyester support to 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. 3
No. 07, No. 3,761,299, British Patent No. 997.0
No. 93, JP-A-53-129262, etc. can be used.

The pressure during glow discharge is 0.005 to 20 T o rr
1, 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 stable fixing glow discharge occurs between ~5000V. A particularly suitable voltage range for improving adhesion is 200
It is 0-4000V.

Furthermore, as seen in the prior art, the discharge frequency ranges from DC to several 1000100O, preferably from 50H2 to 20
MHz is appropriate. Regarding the discharge treatment strength, 0.0 IKV-A・min/d is required because the desired adhesive performance can be obtained.
~5KV-A, min/d, preferably 0.05KV-A・
Minutes/rrr to IKv・A・minutes/bo are suitable.

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

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, butanediol, neopentylene gelyl, 1゜4-cyclohexanediol, 1,4-cyclohexane dimethanol, 1.4-bis-1-oxybenzene, bisphenol A1 diethylene glycol. , polyethylene glycol, etc.

Among the polyesters made of these components, polyethylene terrescrete is the most convenient from the viewpoint of easy availability.

There is no particular limit to the thickness of polyester, but it is approximately 12μ.
A thickness of about 200 μm, preferably about 40 μm to 180 μm 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 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 2X per mole of silver in an aqueous gelatin solution kept at 50°C.
In the presence of 10-' moles of rhodium chloride, an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to obtain an average particle size of 0.
A 2μ silver chlorobromide monodisperse emulsion was prepared. (Cβ composition 95
(mol%) This emulsion was desalted by the flocculation method, 1 mg of thiourea dioxide and 0.6 mg of chloroauric acid were added per mole of silver, and aged at 65°C until the highest performance was obtained. gave rise to

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

n-C+Jzs N0z 2X10-' mol/Ag1 mol lXl0-3 mol/Ag1 mol 4X10-' mol/Ag1 mol KBr 20mg/n
? Polystyrene sulfonic acid sodium salt 40mg/n
(2,6-dichloro-6-hydroxy-1,3,5) This coating solution was coated to give a coated silver amount of 3.5 g/ld.

(2) Protective layer 1 prescription gelatin 1.5g/n (SiO
2 fine particles (average particle size 4 μ) 50 mg/rrl Dodecylbenzenesulfonic acid sodium salt 50 mg/IH 5-nitroimidazole 15 mg/rrr1.
3-divinylsulfonyl-2 propyl 50mg/n
f N-perfluorooctanesulfonyl-N=probylglycinepotadium salt 2mg/Ipolymer-2 (average particle size 0.06μ) 300mg/rd (3) Bank layer prescription gelatin 2.5g/m5O3K
SO:lK S'hK 5OJ SO,K SO, ni80
mg / 1,3-divinylsulfonyl-2propyl 150m
g/rrr Polymer 2 (average particle size 0.06 μ) 900 mg/Idohexyl α sulfosacnate sodium salt 10 m
g/rd Dodecylhenzensulfonic acid sodium salt 35 mg g
/rd (4) Protective layer 2 prescription gelatin 0.8g/% polymethyl methacrylate fine particles (average particle size 3μ)
20mg/Idihexyl alpha sulfosacnate sodium salt 10mg/m Dodecylhenzensulfonic acid sodium salt 10mg/n
(After applying 40 mg/rd of sodium acetate and drying, it was packaged in a moisture-proof bag under the conditions shown in Table 1. As a comparative sample moisture-proof bag, the example of JP-A-61-189936 was used.
Invention 8 disclosed in No. 1 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 BIl- were drilled in the sample at an interval of 200 fins, and after leaving it in a room at 25°C and 30% RH,
The spacing between the two holes was accurately measured using a pin gauge with 1000+n accuracy. Let the length at this time be X. Then, after developing, fixing, washing with water, and drying using an automatic developing machine, the size after 5 minutes is defined as Ymm. 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 done using Fuji Photo Film Co., Ltd.'s FG-660 automatic processor, and the developer and fixer were GRD-1 and GRF made by the same company.
-1 under the treatment conditions of 38° C. for 20 seconds.

The drying temperature at that time was 45 degrees. The needle load is continuously changed while moving at a speed of 10 dragons/second, and the load (g) at which the membrane breaks (i.e., scratches occur on the sample membrane surface) is measured. did.

(3) Evaluation method of drying property by automatic development processing Size 50
．． When 10 sheets of 8×51cnf film were continuously processed in an environment of 30° C. and 80% RH, 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 humidity 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 diagram.

To measure relative humidity, use a thermohygrometer MODEL IIN-L.
Relative humidity was measured using an IEHUMI-TEMP RECODER (manufactured by Chino ■) (sensor HN-L20 (manufactured by Chino ■), and the absolute humidity was converted from the results using an psychrometric chart.

(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 Dimensional changes due to treatment (2) wet film strength, and (3) drying properties by automatic processor treatment were evaluated in the same manner as in Comparative Example.

(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 I, ① and ②.

Solution I: 300ml of water, 79g of gelatin Solution ■: AgN0: + 100g, 400mj of water! ■Liquid; NaCj! 37g, (NH4) 3 Rh C1lb
0.66 mg, 400 ml of water. Solutions (2) and (2) were simultaneously added at a constant rate to Solution I kept at 40°C. After removing soluble salts from this emulsion by a conventional method well known in the art, gelatin is added and 6-methyl-4-hydroxy-1,3,3a+ 7- is added as a stabilizer.
Chitraazaindene and 4-hydroni-1-cy5.6-
1-Rimethylene-1,3°3a,7-thitraazaindene was added.

This emulsion is a monodispersed emulsion with an average grain size of 0.15μ, and the amount of gelatin contained per IKg of emulsion yield is 6
It was 0g.

The following compounds were added to the emulsion thus obtained.

So, Na Polystyrene sulfonic acid sodium salt 10 mg/n (Compound example 1 3) 270 mg/rd Polymer 2 (average particle size 0.06 μ) 500 mg/rd I O2 0.3 mg/rrr Coating amount of silver using the coating solution thus obtained It was applied at a rate of 3 g/rd.

(2) Protective layer l prescription gelatin 1.5g/r+ (polymethyl methacrylate-1 fine particles (average particle size 3μ>
50mg/%03Na Dodecylbenzenesulfonic acid sodium salt 25mg/r
rr dihexyl alpha sulfosacnate sodium salt 10mg/
rrr N-perfluorooctanesulfonyl N-7'' lopylglycine potassium salt 2 mg/rd polystyrene sulfonic acid sodium salt 3 mg/Ipolymer 2 (average particle size 0.06 μ) 200 mg/n (colloidal silica 350 mg/rd riboic acid 3mg/rtr
(3) Bank layer prescription gelatin 2 g/rdSO
3K 5OJ SOJ S03 at 180 mg/n (SOJ 5OsK dihexyl alpha sulfosacna monosodium salt 20 mg/sodium idecylbenzenesulfonate 30 mg/rr
r Polystyrene sulfonic acid sodium salt 30 mg/m Compound Example 1-3) 270 mg/rrr Polymer 2 (average particle size 0.06 μ) 200 mg/r+f (4) Protective layer 2 prescription gelatin 1 g/g polymethyl methacrylate fine particles ( Average particle size 3μ)
40 mg/dihexyl sulfosacnate sodium salt 10 mg/rd Dodecylbenzenesulfonic acid sodium salt 30 mg/r
rr Polystyrene sulfonic acid sodium salt 25 mg/ffl Sodium acetate 30 mg/
rd (Example-3) A 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 pieces were fixed on an insulating plate at intervals of 0 cm.

Fix this electrode plate in a vacuum tank, and
30 mm in thickness 100μ on a rod 5cm apart and directly facing the electrode surface.
cm biaxially stretched polyethylene terephthalate film was run at a speed of 20 m/min. Immediately before the film passes over the electrode, the film is placed in a temperature controller 1-1 with a diameter of 50 cm.
A heating roll with a roller was set at 120° C., and the heating roll was arranged so as to contact each other for 3/4 of a turn. Glow discharge was carried out by applying 2000 m Torr to the above electrode while maintaining the inside of the tank at 0 and I Torr.
This was done by applying a voltage of V. At this time, the electrode current was 0.5A. At this time, the PET support is 0.1
This results in a treatment of 25 KVA min/m'. 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. It was applied and dried at a temperature of 120°C.

Furthermore, apply 20ml of the following prescription coating solution as a second undercoat layer on top of that.
It was coated at a ratio of 1/rd 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 (4,01) 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 1Xl0-5 mol of rhodium per Ag/mol was used as a stabilizer without chemical ripening. Hydroxy-6-methyl-13,3a,7-chitrazaindene was added.

This emulsion contains a tetrazolium salt. was added at 5×10 −″ moles per mole of Ag.

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

This emulsion was coated with a silver amount of 3.9 g/% and a gelatin amount of 3.1
It was applied so that the ratio was g/rrl.

(2) Developer formulation ethylenediaminetetraacetic acid disodium salt (dihydrate)
0.75g anhydrous potassium sulfite
51.7g anhydrous potassium carbonate
60.4. g Hydroquinone
15.1g 1-phenyl-3-pyrazolidone 0.51g Sodium bromide 2.2g 5-methylbenztriazole 0.124g 1-phenyl-5-mercaptotetrazole 0.018
g 5-nitro-indazole 0.106g diethylene glycol 98g Add water I I
l (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 in Example-1.
1 was created.

Sample 501 showed good results similar to sample 101.

Binder: Gelatin 1 g/m Polymer latex 0.16 g/m+C41z-C
H+-I-r +Ctb-CH+yr-(CHz)
zsOsK (CHz) 24 to zsO3
mg/m (CH2) 2SO3K (CH2) 2S
15mg/rr in 03? Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Date: 1986

Claims (1)

[Scope of Claims] 1) In a silver halide photographic 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%. General formula (I) of a silver halide photographic material, which is dried at the following relative humidity and stored in an atmosphere with an absolute humidity of 1% or less: ▲Mathematical formula, chemical formula, table etc. ▼ R^1, R^2, R^3 and R^4 and carbon number 1 to 20
an alkyl group having 6 to 20 carbon atoms, or an aryl group having 5 to 20 carbon atoms, which may be the same or different. Furthermore, R^1, R^2, R^3, and R^4 may have a substituent, or any two of them may combine to form a ring. X represents a group capable of leaving when the compound represented by the general formula (I) reacts with a nucleophilic reagent. Y^■ represents an anion. 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.