JPH1172866A - Silver halide photographic composition protected against formation of yellow fog - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic compsn. protected against formation of yellow fog. SOLUTION: This photosensitive silver halide photographic material consists of a supporting body, one or more water-permeable photosensitive silver halide layers on one or both surfaces of the supporting body, and an outermost protective stress-resistant layer. Each layer of the photographic material above described contains a nonion polyoxyalkylene compd. by >=0 to <5 mg/m<2> . The protective stress-resistant layer and/or the photosensitive layer contain an ionic polyoxyalkylene compd. The photographic material has <1×10<10> Ω/m<2> surface resistance in the transverse direction measured according to DIN53482.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates to silver halide photographic compositions, and more particularly to radiographic materials containing additives that improve the stability to yellow fog.

[0002]

BACKGROUND OF THE INVENTION The formation of yellow fog in light-sensitive silver halide photographic materials is most commonly known to those skilled in the art as a problem associated with the presence of fine silver nuclei. Before the production of the silver salt present in the emulsion layer and / or the outermost layer of said material,
These nuclei, which are produced during the production or by post-production reduction, then occur as particles. In the special case where silver halide light-sensitive photographic materials are susceptible to yellowing after storage, the cause is almost always formed by the reduction in a somewhat fatigued developer at the surface of the treated material where physical development of silver ions occurs. Is required to cause the phenomenon of adsorption of fine silver particles. The most common cause of the yellowing phenomenon is the deposition of fine silver in a non-photosensitive colloid layer coated in a water permeable relationship with the photosensitive emulsion layer.

In order to prevent yellowing of such a silver halide photosensitive photographic material, the molten silver salt is reduced on silver nuclei by physical development, particularly when the developer contains a silver halide solvent. The presence of, for example, chloride ions in a fatigued developer after development of a silver halide photographic material containing an emulsion rich in silver chloride is described, for example, in US Pat. No. 3,362,826,336402.
As disclosed in US Pat. Nos. 8,3365294 and 36000178, this leads to special measures in which the used chemical additives are incorporated into a non-photosensitive, water-permeable colloid layer.

[0004] Photosensitive silver halide materials for radiography often are coated with large amounts of silver per square meter to reach the required speed. Processing in an automatic processor provided with replenishment means and / or fatigue of the developer and fixer when poorly soluble but more sensitive emulsions rich in silver bromide and / or silver bromoiodide are used. To avoid the problem of (and excessive formation of silver salt dissolved ions), the problem is not encountered. Although the rapid processing using smaller volumes of replenisher solution in the last decade has been of conventional interest, the severe problem of yellow stains or yellow fogging has been found especially in the (Patent) literature. Not stated. Today, there is a trend which nevertheless favors the use of silver halide emulsions having chloride-rich crystals.

[0005] In some special cases, however, the problem of "yellowing" can occur. When unexposed radiographic film materials are stored in extremely harsh atmospheric environments of temperature and humidity, such as in tropical geographic regions, non-automated dish development (this method is also called dish or scale development, (Still done by the customer) leads to the "yellowing" problem. In such special cases,
It is clear that there is no automatic replenishment and that development is often done in a tired developer.

Furthermore, if the interleaving paper is used between continuous films stacked in a package to avoid surface damage and sticking of said films which come into contact with each other under the severe storage conditions described above, And / or if the film is cured to a lower degree to avoid speed loss, the problem of "yellowing" or "yellow stain" will be more severe. Such undesired stains often appear in the form of fibrous structures in the slip-sheets or spacers of the radiation film material, which consequently hinders a proper and clear medical diagnosis.

[0007]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide light-sensitive photographic material free from yellowing or yellow stain after processing.

In particular, it is an object of the present invention to avoid that the fiber structure of the interleaving paper present between the film materials stacked in a wrapped state appears as yellowing or yellow stain.

It is a further object of the present invention to avoid the aforementioned yellowing or yellow stain even after storage of the unexposed material in a high temperature and high relative humidity environment.

[0010]

SUMMARY OF THE INVENTION To achieve the objects of the present invention, a photosensitizer comprising a support, one or more water-permeable photosensitive silver halide layers on one or both sides of the support, and a protective stress-resistant layer. A silver halide photographic material, wherein each layer of the material contains a nonionic polyoxyalkylene compound in an amount of 0 to less than 5 mg / m ² , wherein the protective stress-resistant layer and / or the photosensitive layer A polyoxyalkylene compound, wherein the material has a D less than 1 × 10 ¹⁰ ohm / square;
There is provided a photosensitive silver halide photographic material having a lateral surface resistance measured as defined in IN53482.

When an after layer is present, the after layer does not contain a polyoxyalkylene compound.

[0012]

DETAILED DESCRIPTION OF THE INVENTION An essential feature of the present invention is that the support and one or more water-permeable coatings (one-sided or double-sided) coated on one side (one-sided) or on both sides thereof <1 × 10 ¹⁰ ohm / square measured as specified in DIN 53482 for a photosensitive silver halide photographic material having a layer arrangement comprising a hydrophilic and hydrophilic photosensitive silver halide layer, a protective layer and optionally an after layer. Is to obtain the lateral surface resistance.

The use of nonionic polyalkylene surfactants having antistatic properties in protective stress-resistant layers of photographic materials as antistatic agents, as described, for example, in EP-A 0 644 456 and the corresponding US Pat. No. 5,560,132. It is common to do. In the material of the present invention, each hydrophilic layer of the material contains a nonionic polyoxyalkylene compound in an amount of 0 to less than 5 mg / m ² , more preferably 0 to less than 3 mg / m ² . It is an essential feature of the present invention that all layers of the photographic material are "substantially free" of said nonionic polyoxyalkylene compound, in which case the presence of trace amounts as represented herein is still acceptable. However, it is preferable that the nonionic compound is not contained at all.

Examples of such nonionic polyoxyalkylenes which should be present in minute amounts in each of the hydrophilic water-permeable layers of the single- or double-coated radiographic material of the present invention and whose presence should still be avoided For example, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ether or polyethylene glycol alkyl aryl ether, polyethylene glycol ester, polyethylene glycol sorbitan ester, polyalkylene glycol alkylamine or alkylamide, silicone-polyethylene oxide adduct, glycidol Derivatives, fatty acid esters of polyhydric alcohols, and alkyl esters of saccharides.

In particular, the following compounds should be avoided: Phen-OC ₂ H ₄ —O—CH ₂ —O—CH ₂ —O— (C ₂ H ₄ —O—CH ₂ ) _n —C ₂ H _{4 -O-CH 3 (Ia) H} 3 CO- (CH 2) 4 - (O- (CH 2) 4 -O) n - (CH 2) 4 - (OC 2 H 4 -O-CH 2) m - _{OC 2 H 4 -OH (Ib)} HO-C 2 H 4 - (OC 2 H 4 -O-CH 2) n -ORO- (CH 2 -OC 2 H 4 -O) n -C 2 H 4 -OH (Ic) wherein n and m are at least 4, more preferably 8 to 3
An integer having a value of 0, wherein R represents a long-chain (substituted or unsubstituted) alkyl or alkylaryl group having at least 10 carbon atoms such as, for example, oleyl;
Represents a substituted or unsubstituted phenyl.

[0016] Non-ionic polyoxyalkylene compounds having a fluorinated alkyl chain are also excluded. N-polyoxyethylene ethyl perfluorocaprylic acid amide compounds corresponding to formula (II), for example having caprylic acid amide as terminal group, are to be particularly avoided. _{C 7 F 15 CONH- (C 2} H 4) - (OC 2 H 4) 17 -OH (II)

Investigation of non-ionic polyalkylene compounds
Research Disclosure 36544 (September 1994)
Chapter IX and Research Disclosure 38957 (19
(September 1996).

However, it is not always possible to completely avoid the presence of polyoxyalkylene compounds in one or more layers of the photographic material according to the invention. Indeed, the coating solution may contain a nonionic polyoxyalkylene compound as a preferred surfactant, or may contain said compound as a minor impurity.

In order to achieve the above-mentioned object of the present invention, an ionic polyoxyalkylene compound is used in one or more layers of the photographic material of the present invention instead of the previously discussed nonionic polyoxyalkylene compound. Is preferred.

A particularly preferred ionic polyoxyalkylene compound is C ₈ H ₁₇ -Phen- (O—C ₂ H ₄ ) ₈ —CH ₂ —COONa (III)

As the ionic surfactant having an antistatic property, a well-known polyoxyalkylene compound having an ionizable group such as a carboxylic acid or sulfonic acid group may be used in the protective stress-resistant layer. Formula (III) (wherein Phen
Represents "phenyl") are very typical and may therefore be further substituted,
It may not be replaced. A reference on that is Resear
ch Disclosure 36544 (September 1994) and 38
957 (September 1996) in a survey of Chapter IX.

In one embodiment of the invention, the one or more ionic polyoxyalkylene compounds are present in a protective stress-resistant layer and / or in one or more photosensitive silver halide emulsion layers, with a maximum amount of 30 mg / m2. Less than ² , more preferably 10-2
5 mg / ^{m 2,} and even more preferably 10-20mg
/ M ² .

As hydrophilic colloid binders present in the hydrophilic layer of the photographic material according to the invention, protein colloids (eg gelatin), polysaccharides (eg (potato) starch), and synthetic substitutes (eg polyvinyl alcohol, poly- N-vinylpyrrolidone, polyvinylimidazole, polyvinylpyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof) can be used. Another preferred substitute is a colloidal silica sol. Furthermore, the use of mixtures of said hydrophilic colloids is not excluded. The most preferred of these binders is gelatin. Conventional lime-treated or acid-treated gelatin can also be used. The preparation of such gelatin forms is described, for example, in "The Science and Technology of Gelatin", AG
Ward and A. Courts, Academic Press 1977, 29
It is described on page 5 and the next page. Gelatin is Bull. Soc.
Enzyme-treated gelatin described in Sci. Phot. Japan, No. 16, page 30 (1966). However, to minimize the amount of binder, the gelatin can be partially or totally replaced by the synthetic polymers described above or natural or semi-synthetic polymers. Natural substitutes for gelatin are, for example, zein, albumin and casein, cellulose, saccharides, starch, and other proteins such as alginates. Semi-synthetic substitutes for gelatin are, for example, gelatin derivatives obtained by converting gelatin with an alkylating or acrylating agent, or by grafting a polymerizable monomer to gelatin, and hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, And modified natural products such as cellulose derivatives of cellulose sulfate.

If the after layer is on top of the outermost protective layer, for whatever reason, the silver halide photographic material of the present invention should not contain any hydrophobic or hydrophilic polyoxyalkylene compounds at all.

US-A 4301240 and US-A
The ionic cross-linked copolymer known from 5561032 may be present during the protective stress-resistant application of the material according to the invention. The preferred latex used therein is a crosslinked polymer latex, which comprises 1 to 10 mol% of tetraallyloxyethane units as multifunctional crosslinking monomers, and 90 to 99 mol% of acrylate and / or methacrylate units. Containing acrylic acid and / or
Or a copolymer of methacrylic acid esters, wherein at least 75% of the ester groups in said copolymer have been converted to alkali metal carboxylate groups and thus exhibit ionic properties. A particularly preferred latex of the crosslinked ionic polymer is a poly ([c.
l.] tetra-allyloxy-ethane-co-methyl acrylate / acrylic acid). The following polymer or monomer copolymer combinations, whether in combination with the crosslinked copolymers described above, have been found to be extremely useful as ionic or nonionic polymers: polyvinylpyrrolidone, polyacrylamide, polyacrylic acid , Polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, and styrene-maleic acid or styrene-maleic anhydride copolymers. The crosslinked copolymer is at least 10% based on the amount of hydrophilic colloid present in the stress-resistant layer.
It is applied in an amount of% by weight.

Further, the latex-type copolymer may be present during the application of the gelatin-free outermost layer applied to the stress-resistant layer.

The presence of at least one or more ionic or non-ionic polymer or copolymer latex in the protective stress-resistant coating and, optionally, the after-layer applied thereto as described in US Pat. It provides good retention of charging properties, the absence of water spots in the dried film after processing, and the appearance of improved surface glare. A similar advantage is recognizable with thin coatings for application in more rapid processing conditions, and the appearance of sludge during processing is significant in hardening-free processing solutions as well as in hardening-free processing solutions. To decrease.

The protective stress-resistant layer and the after-layer (if present) may further comprise coating aids such as, for example, perfluorinated surfactant wetting agents and spacing agents. Spacing agents that may also be present in the protective stress-resistant layer are generally 0.1%.
It has an average particle size of 2-10 μm. Spacing agents can be alkali-soluble or insoluble. Alkali-insoluble spacing agents usually remain permanently in the photographic material, while alkali-soluble spacing agents are usually removed therefrom in an alkaline processing bath. Suitable spacing agents are made from polymethyl methacrylate, a copolymer of acrylic acid and methyl methacrylate, and hydroxypropyl methylcellulose hexahydrophthalate. Other suitable spacing agents are US-A 46
14708.

The preferred protective stress-resistant layer is 2.5 g at 38 ° C.
Made from gelatin hardened to a degree corresponding to a water absorption of less than / m ² . Application of gelatin in the protective layer is preferably not more than 1.20 g / ^{m 2,} more preferably in the range of 0.60-1.20g / ^{m 2.}

In a preferred embodiment, the gelatin in the stress-resistant layer is partially replaced by colloidal silica. Colloidal silica provides a further improvement in physical properties. Preferably colloidal silica having an average particle size of less than 10 nm and a surface area of at least 300 m ² / g is used, the colloidal silica being at least 50 m ² / g
It is applied in an amount of g / ^{m 2.} Furthermore, the application of said colloidal silica in the stress-resistant layer is preferably 50-500 mg / m ²
In the range. Particularly good results in full accordance with the present invention are obtained by using a stress-resistant layer comprising at least 50% by weight of colloidal silica, based on the preferred ionic polymer latex described above. Especially preferred colloidal silica particles have an average particle size of less than the surface area and 7nm of 500m ² / g. This type of silica is known as KIESELSOL 50
0 (KIESELSOL is a registered trademark of Bayer AG, Leverkusen, Germany).

In a mixture with hardened gelatin, the stress-resistant layer may further reduce the tendency of the layer to stick, especially in high relative humidity atmospheres, by dispersing wax particles (carnauba wax or montan wax) or polyethylene particles, fluorinated It may further comprise a friction reducing substance such as polymer particles, silicone polymer particles and the like.

The gelatin binder can be previously hardened using a suitable hardener. Such curing agents are of the epoxide type, the ethyleneimine type, the vinylsulfone type, for example, 1,3-vinyl-sulfonyl-2-
Propanol, chromium salts such as chromium acetate and chromium alum, aldehydes such as formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin, dioxane derivatives such as 2,3-
Dihydroxy-dioxane, active vinyl compound such as 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compound such as 2,4-dichloro-6-hydroxy-s-triazine, and mucohalic acid such as mucochlor Acid and mucofenoxycyclolic acid. These curing agents can be used alone or in combination. The binder is also a carbamoylpyridinium salt disclosed in U.S. Pat. No. 4,063,952 and EP-A0.
It can be cured with a rapidly reacting curing agent such as the onium compounds disclosed in US Pat.

In another embodiment of the present invention, the presence of a mercapto compound and / or a polyhydroxybenzene compound in the protective layer of the light-sensitive silver halide photographic material according to the present invention is particularly preferred because it eliminates any risk of yellowing. .

The compounds, if present, are each present at 0.01-10 mg / m ² , more preferably at 0.0
4-4 mg / m ² and / or 2.5-250 m
g / m < ² >, more preferably 1-100 mg / m < ² >, is added to the coating compound of the protective stress-resistant layer.

Preferred mercapto compounds are unsubstituted or substituted mercaptotetrazole compounds such as, for example, 1-phenyl-5-mercaptotetrazole, in which case if substituted, for example, a carboxyl group or a sulfone group (but not limited thereto) Particularly preferred are substituents which render the compound soluble in alkaline media, such as

Preferred polyhydroxybenzene compounds are unsubstituted or substituted dihydroxybenzene compounds, with dihydroxybenzene disulfate being a particularly preferred compound.

Typical supports for photographic silver halide emulsion materials are hydrophobic resin supports or paper supports coated with a hydrophobic resin. Hydrophobic resin supports are well known to those skilled in the art,
For example, polyester, polystyrene, polyvinyl chloride,
It is made from polycarbonate, preferably from polyethylene terephthalate or polyethylene naphthalate.

The hydrophobic resin support is usually provided with one or more hydrophobic subbing layers known to those skilled in the art to adhere to the hydrophilic colloid layer. Suitable subbing layers for polyethylene terephthalate are for example US-A 3,397,988,36.
49336, 4123278 and 4478907.

The light-sensitive silver halide photographic material according to the present invention has a DIN 5348 to sufficiently achieve the object of the present invention.
It has a lateral surface resistance of less than 1 × 10 ¹⁰ ohms / square, more preferably less than 1 × 10 ⁹ ohms / square, as measured by the method specified in 2. In addition to the good adhesion properties between the hydrophilic photosensitive layer of the material according to the invention and the support, D
In order to obtain such a low lateral surface resistance as measured by the method described in IN 53482, the presence of an undercoat layer in contact with the support and a hydrophilic colloid layer applied thereon is particularly preferred, in a preferred embodiment the The hydrophobic subbing layer comprises vinylidene chloride, and in a further preferred embodiment of the invention said subbing layer comprises a polythiophene compound as a particularly suitable antistatic agent having electrical conductivity. In particular for the materials according to the invention, for example, US Pat.
As disclosed in US Pat. Nos. 681 and 5391472, the polyethylene dioxythiophene compound should be in a subbing layer coated on the support.

According to the invention, the material is thus on one or both sides of the support and has a subbing layer adhering to the support, said subbing layer further comprising vinylidene chloride and a polyethylenedioxythiophene compound.

In a further preferred embodiment, the hydrophilic colloid layer applied on the subbing layer of the material according to the invention is a gelatinous layer having gelatin preferably in an amount of 0.1-0.3 g / m ² , which is Corresponds to a fairly thin interlayer between the photosensitive silver halide emulsion layer and the subbing layer.

The intermediate layer may include one or more antihalation dyes. Halation spinning dyes are non-spectral sensitizing dyes widely used in photographic materials to absorb reflected and scattered light. Examples of the dye include, for example, US-
A 3560214, 4857446, 534474
9, 5478708, 5502205.

The filter dye is EP-A 040170.
9; 0384633; 0323729; 027472
3: 0276566; 0351593; and US-A
4900653; 490565; 4949954; 4
940654; 4948717; 4988611 and 4
803150; and Research Disclosure 19551
(July 1980) in a layer of a photographic material of the type described in (but not limited to these examples).

The light-sensitive silver halide photographic material according to the present invention is coated with at least one light-sensitive silver halide emulsion layer.

The silver halide emulsion present in the emulsion layer may be of any crystal habit (for example, cubic, octahedral, tabular or irregular, with or without round edges, with projections, epitaxy deposits). Or not) and any silver halide composition (eg, silver bromide, silver bromoiodide, silver bromochloride, silver bromochloroiodide, silver chloride, silver chlorobromide, silver chlorobromoiodide, silver chloroiodide) And silver halide emulsion crystals having the formula:

Emulsions containing crystals having a tabular habit of {100} or {111} major faces are preferred. The crystals are 0.
An average crystal thickness of less than 3 μm and an average aspect ratio of 2 or more, more preferably a thickness of less than 0.2 μm and 5 or more,
Even more preferably, it has an average aspect ratio of 8 or more. Tabular crystals have at least 5 of the total projected area of said crystals.
Occupies 0%. More preferably there are silver bromoiodide crystals having an iodine concentration of 1 mol% or less, said crystals having a coefficient of variation of less than 25%, more preferably 10-20%.

Mixtures of the emulsions are described, for example, in EP-A 0770
As described in 909, crystals having different compositions and / or crystal habits may be present in one or more emulsion layers.

The total amount of silver halide expressed in silver nitrate equivalents per square meter and per side is preferably 3-5.
g, more preferably 3.5-4.5 g.

If an after-layer is present, the application of the gelatin-free after-layer may be performed by any coating technique known to those skilled in the art, as is the application of the protective stress-resistant layer and the photosensitive emulsion layer. Examples of such coatings are doctor blade coating, air knife coating, flow coating, slide hopper coating or meniscus coating, which are the coating techniques known in the manufacture of photographic silver emulsion layer materials. Flow coating and slide hopper coating are, for example, EP-
A 0752617. US-A 42
The spray application technique known in 18533 may be applied, for example, when applying an after layer.

Any thickener can be used to adjust the viscosity of the solution used in any of the above coating techniques, provided that the coating technique does not particularly affect the photographic properties of the silver halide photosensitive photographic material. . Preferred thickeners are polystyrene sulfonic acid, sulfonic acid ester, polysaccharide, polymer having sulfonic acid group, carboxylic acid group or phosphoric acid group, polyacrylamide, polymethacrylic acid or a salt thereof, acrylamide and methacrylic acid and a salt derived therefrom. , 2-acrylamido-2-methyl-propanesulfonic acid, polyvinyl alcohol, alginate, xanthan, carrageenan and the like.

Polymeric thickeners known from the literature that result in thickening of the coating solution can be used independently or in combination. Patents relating to thickeners include US-A 31,674.
10, Belgian Patent No. 558.143, JP-A No
s. 53-18687 and 58-36768 and DE 3
869945. EP-A as a particularly important thickener
Synthetic clays such as those described in 0813105 can be used.

In a preferred embodiment according to the invention, the light-sensitive silver halide photographic material is a single-coated or double-coated radiographic material.

In addition to the advantages associated with the formation of static charge and the absence of yellow fog in the particular environment described in the present invention,
The materials according to the invention also have the advantage that the side of the silver halide emulsion layer is in contact with the rear side of the recording material and that hydrophobic polymeric binders and rubbers (for example for binder components of phosphor screens used as X-ray intensifying screens and the like) Obviously, it provides friction with substances such as For example, during the loading of film into a cassette (eg, an X-ray cassette) or camera, or during the taking or projection of a series of photographs, such as occurs with an automatic camera or film projector, the formation of electrostatic charge and the resulting dust collection and / or dust. Parking is thus prevented.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0055]

【Example】

6.1.1. A support coated with a subbing layer and covered with a gelatin layer.

A bluish, laterally stretched polyethylene terephthalate film support of about 0.61 μm thickness was primed on both sides with a coating solution at a coverage of 130 m ² / l (as comparative undercoat layer) "SUBCOMP"). The following formulations were used per square meter per side for the subbing layer "SUBCOMP":

0.17 g of a latex copolymer of vinylidene chloride (88% by weight), methyl acrylate (10% by weight) and itaconic acid (2% by weight), methyl methacrylate (47.5% by weight), 1,3
0.06 g of a latex copolymer of butadiene (47.5% by weight) and itaconic acid (2% by weight); 0.001 g of polymethyl methacrylate particles having an average diameter of 3.5 μm as matting agent; and as a coating aid. 0.001g of HOSTAPAL BV (HOECH
ST AG) and 0.003g of AKYPO OP 80 (CHEMY). (1
AKYP commercially available as a 00% pure polymer compound
O OP 80 has Phenyl-C (CH ₃ ) ₂ -CH ₂ -C (CH
₃ ) A polyoxyethylene compound having _three groups and a carboxylic acid group; HOSTAPAL BV has a sulfonic acid group (in the form of a sodium salt) as one terminal group and 2,4,6-tri- as another terminal group. _{[CH (CH 3) (C} 2 H 5)] - Phenyl group available as a 50% aqueous solution of polyethylene compound having a. )

The layers were dried with a stream of hot air, after which the coated support was stretched transversely at a temperature of about 110 ° C. by 3.5 times its original width.

The final thickness of the film was 175 μm. The film was then heat set for about 10 seconds while maintaining under tension at a temperature of 220 ° C.

After heat setting, the film was cooled.

The priming process for the material according to the invention (designated "SUBTHIO") was similar, with the following layer composition per square meter per side: vinylidene chloride (88% by weight), methyl acrylate ( 0.48 g of a copolymer of 10% by weight) and itaconic acid (2% by weight), methyl methacrylate (47.5% by weight), 1,3
0.06 g of a copolymer of butadiene (47.5% by weight) and itaconic acid (2% by weight), silica particles (Kieselsol 100F, Bayer as matting agent)
AG, Leverkusen, Germany) 0.1 g of poly-3,4-ethylenedioxythiophene-polystyrenesulphonic acid and 0.1 g of sorbitol.

The composition (expressed in quantities per square meter) of the gelatin layer covering the subbing layer was as follows: gelatin (Rousselot type R10985) 0.20
g, silica particles (Kieselsol 300F, Bayer AG) 0.18
g, 13 m of ULTRAVON W (CIBA-GEIGY) as a coating aid
g, 7 mg of ARKOPAL NO60 (HOECHST AG) and 67 mg of trimethylolpropane, and 1 mg of polymethyl methacrylate (mean particle diameter: 2.5 μm) as matting agent. ULTRAVON W is a mixture of sulfonic acid sodium salt substituted benzimidazole compounds in which the 2-position between two N-atoms is C ₁₇
Substituted with an H ₃₅ -group, wherein the compound has one N-
Atoms are partially substituted by benzyl groups, which are further partially substituted by sodium sulfonate bases; ARKOPAL NO60 is a polyethylene having a C ₉ H ₁₉ -substituted phenyl group as one terminal group. Glycol.

6.1.2. Preparation of Coating Solution for Emulsion Layer (EM)

1.2.1. Production of emulsion.

A tabular silver bromoiodide emulsion containing 1 mol% AgI and 99 mol% AgBr was precipitated using the double jet method as described in US Pat. No. 5,595,864.

Excess KNO ₃ was removed by flocculation and washing after precipitation. The tabular grain emulsion thus obtained containing 75 grams of gelatin per mole of AgNO ₃ had the following properties: average diameter of a circle with the same projected area of the tabular grains:
1.12 ± 0.23 μm (0.23 = standard deviation s). Average thickness of tabular grains: 0.23 μm. -Aspect ratio: 5.5. The proportion of the total projected area covered by the tabular grains: 9
8%.

1.2.2. Chemical sensitization.

This emulsion was formulated with potassium thiocyanate, sodium thiosulfate, chloroauric acid, and -5,5'-dichloroanhydride to obtain an optimized fog-sensitivity relationship.
Chemically sensitized in the presence of 3,3'-bis (n.sulfobutyl) -9-ethyloxacarbocyanine hydroxide.

1.2.3. Additional components of emulsion solution.

The following components were added to the emulsion at 40 ° C. per mole of AgNO ₃ (applied 4.1 g per side and per square meter): 4-hydroxy-6-methyl-1,3,3 3a, 7-
0.29 g of tetraazaindene; 9.1 g of sorbitol; polyethyl acrylate (molecular weight = 100000)
0) 14.5g; - 1,3- dihydroxybenzene 3.05 g; - dextran (molecular weight _{= 10000) 31g; - C 8} H 17 -Phen- (O-C 2 H 4) 8 -CH 2 -COONa
0.42 g;-10 g of gelatin; and-the amount of deionized water required to obtain the desired wet coating thickness.

1.3.1. Composition of protective stress-resistant layer (AS) (compound, expressed in grams per square meter per side): gelatin 1.10 polymethyl methacrylate 0.023 (average particle diameter: 6 μm) 1-p− carboxyphenyl-4,4'-dimethyl-3-pyrazolidine - 1-one _{0.054 C 7 H 15 -CO-NH-} (CH 2 -CH 2 -O-) 17 -H 0.0188 C 8 H 17 - _{Phen- (O-C 2 H 4} ) 8 -CH 2 -COONa 0.004 formaldehyde 0.1

The radiographic material was provided with an after-layer as a gelatin-free outermost layer above the protective stress-resistant layer covering the silver halide emulsion layer described above.

1.3.2. Outermost layer (“After layer” (A
Composition of L)):

The formula R—O— (CH ₂ CH ₂ O) _n —H (where n is 1
0 and R is oleyl) was added to the aqueous solution prepared for application. The compound is 5.0 g /
1 and was applied in an amount of 40.0 mg / m ² . The compound of formula F ₁₅ C ₇ COONH ₄ as a nonionic ammonium perfluoro compound was present therein in an amount of 3 mg / m ² .

A slide hopper coating was used for the simultaneous application of the emulsion layer (EM), protective stress resistant layer (AS) and antistatic after-layer coating (AL). Table 1 below
The material corresponding to Comparative Application No. 13 was stored for 3 days (at 35 ° C. and 80% relative humidity).

C ₈ H ₁₇ -Phen- (O-C ₂ H ₄ ) ₈ -CH ₂ -C
Note that OONa was present in the emulsion layer and the protective stress-resistant layer as an ionic polyoxyalkylene compound. In the absence of it, application failure and irreproducible values of relative surface resistance were observed.

The other materials are the same as Comparative Material No. 13 in the following points.
With the formula RO- (CH₂CH ₂O)_n−H (however
n represents 10 and R represents oleyl)
Mix oxyethylene compound into after layer (AL)
Instead, material No. 14 has a protective stress-resistant layer (AS)
No. 15 mixed into the emulsion layer (EM)
Was.

For material No. 1-12, no after layer was applied and in Table 1 the compound R--O-(CH
A polyoxyethylene compound represented by ₂ CH ₂ O) _n -H (where n represents 10 and R represents oleyl) was mixed into the protective stress-resistant layer.

Material Nos. 7-12 are different from the materials in that Compound A is present in the protective stress-resistant layer as a polyoxyethylene compound.
No. 1-6 was different. On the other hand, in the material No. 1-6, the compound B, that is, the compound of the formula C ₇ F ₁₅ CONH- (C ₂ H ₄ )-(OC ₂
H _{4) 17} corresponds to -OH N-polyoxyethylene ethyl perfluoro caprylic acid amide was used.

The amounts of mg / m ² per side of the polyoxyethylene compound A or B are given in Table 1.

A further difference is that material No. 4 on both sides of the support was used.
6 and 10-12 (in Table 1, "SUBTHI
O ", indicating the presence of the polythiophene compound in the undercoat layer containing vinylidene chloride as indicated above) and the undercoat layer from materials Nos. 1-3, 7-9 and 13-15 ( In Table 1 is referred to as a "SUBCOMP", Porichiofu
Composition of the undercoat layer SUBCOMP (comparative undercoat layer) containing no ene compound .

As an objective evaluation of antistatic properties, ohm /
The lateral surface resistance in squares was measured before treatment at a relative humidity RH of 30%, as specified in DIN 53482.

The following tests were performed to control the presence of "yellow fog" or "yellow stain" on the processed film.

The entire package, including ten stacked film sheets (14 "x 17") separated by slips, was placed between the cardboards. This package was further inserted into a light-tight plastic bag. A conditioning room with a temperature of 60 ° C. and 11% relative humidity (“clima chambe”) to mimic the real environment in which the customer is working
In r) "), this plastic bag was stored for 7 days. A 2.8 kg polyvinyl chloride plate covering the entire bag surface was placed on the plastic bag.

For processing the stored film sheet,
The following developers and fixers were used.

Per liter of developer:-8 g of hydroquinone-0.6 g of phenidone-40 g of sodium sulfite-40 g of potassium bromide-1 g of sodium hexametaphosphate-50 g of sodium carbonate

Per liter of fixer: 1 g of tri-sodium sequestrene 130 g of sodium thiosulfate 10 g of sodium sulfite 6 g of sodium carbonate 14 g of sodium hydrogen carbonate

Into the developing tank and the fixing tank each having a capacity of 45 liters, 6.5 liters of the developing solution and 6.5 liters of the fixing solution having the above-mentioned composition were respectively injected. A washing tank filled with tap water was placed between the developing tank and the fixing tank and after the fixing tank. 150 meters ² of the film material in order to fatigue the developer and fixer (14 "× 1
The 1200 "7" film was converted to 4 "so as to mimic the actual processing of a film sheet stored in a" climber chamber "of the actual marginal conditions (causing the problems described in the present invention). Treated for days.

The stored film sheet was developed with a fatigued developer at 29 ° C. for 3 minutes, further washed with a tap water tank for 5 seconds, fixed with a fixing solution for 4 minutes, and washed with a second tap water tank for 5 minutes.

The presence of a “yellow fog” or “yellow stain” after treatment representing the fiber structure of the interleaving paper (sold by INTERMILL'S, Belgium) is indicated in Table 1 by the symbol “+”;
On the other hand, its absence is indicated by the symbol "-".

In addition, the presence of spark exposures detected after the above processing cycle was qualitatively evaluated using a number from "0" (good, no spark) to "5" (extremely bad). (Note that “bad” corresponds to the number “3”). For this purpose, a "climber chamber" (a room with well-defined storage conditions as described above)
10 unexposed sheets measuring 14 ″ × 17 ″ were moved through a “Hitashi Model TU 130V” medical radiographic cassetteless table.

[0092]

[Table 1]

As can be concluded from Table 1, they are stacked between sheets in an atmosphere of high temperature and high relative humidity and have sufficient antistatic properties (transverse surface resistance of less than 1 × 10 ¹⁰ ohm / square). However, it is an object of the present invention to provide a material that does not exhibit yellow fog formation or spark exposure after processing with a fatigued developer (eg, because of no replenishment)
The non-ionic polyoxyalkylene compound in the protective stress-resistant layer and / or the emulsion layer is reduced to a minimum (0 to less than 5 mg / m ² ) and the lateral surface resistance of less than 1 × 10 ¹⁰ ohm / square is DIN 53482. It is only realized if measured before processing as specified in.

While acceptable sensitivity for spark formation is observed in the presence of compound B as a polyoxyalkylene compound having caprylic amide as a terminal group,
The danger of getting a spark still exists. Only if said compound B is present in an amount in the range claimed and the claimed lateral surface resistance is measured as specified in DIN 53482 (as well as the formation of a yellow fog) The danger is completely eliminated.

Composition of Coating Solution for Emulsion Layer (1.2.3)
The risk of sparks and yellow fog is further minimized when more ionic polyoxyalkylene compounds are present, as evidenced by the composition of the stress-resistant layer (1.3.1).

While the preferred embodiment of the invention has been described in detail, it will be apparent to those skilled in the art that various modifications can be made without departing from the scope of the invention as defined in the appended claims. There will be.

Claims (5)

[Claims] A support, one or both sides of said support;
A photosensitive silver halide photographic material comprising the above water-permeable photosensitive silver halide layer and the outermost protective stress-resistant layer, wherein each layer of the material is nonionic in an amount of 0 to less than 5 mg / m ² . The protective stress-resistant layer and / or the photosensitive layer comprises a polyoxyalkylene compound, wherein the protective layer comprises an ionic polyoxyalkylene compound and the material is less than 1 × 10 ¹⁰ ohm / square, as defined in DIN 53482. Silver halide photographic material having a lateral surface resistance as described. 2. The material according to claim 1, wherein said ionic polyoxyalkylene compound is present in an amount of 10-25 mg / m ² . 3. The material according to claim 1, wherein the protective stress-resistant layer further comprises a mercapto compound and / or a polyhydroxybenzene compound. 4. The material according to claim 1, wherein said material has an undercoat layer attached to one or both sides of said support, and said undercoat layer contains vinylidene chloride and a polyethylenedioxythiophene compound. . 5. The method of claim 1, wherein the at least one photosensitive silver halide layer comprises an emulsion having tabular silver halide crystals having an average aspect ratio of 2 or more and an average crystal thickness of less than 0.3 μm, wherein the tabular crystals are 5. The material according to claim 1, which occupies at least 50% of the total projected area of the crystal.