JPH04107449A - Silver halide photographic sensitive material having high image quality - Google Patents

Abstract

PURPOSE:To enhance an antistatic performance and to lessen the generation of the pressure fogging in a processing liquid by incorporating a high boiling solvent having >=150 deg.C b.p. into at least one layer of an antistatic layer, emulsion layers or other hydrophilic colloidal layers. CONSTITUTION:The antistatic layer consisting of the reaction product of a water-soluble conductive polymer, hydrophobic polymer particles and a hardener is provided on at least one side of a base. The high boiling solvent having >=150 deg.C b.p. is incorporated into at least one layer of the antistatic layer, emulsion layers or other hydrophilic colloidal layers. The hydrophobic polymer particles are incorporated therein in order to prevent crazing and cracking. The silver halide photographic sensitive material having the high sensitivity even in rapid processing, the good antistatic performance and the pressure resistance in the liquid is obtd. in this way.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having an antistatic layer and excellent in-liquid pressure resistance. .

[Background of the invention]

In silver halide photographic materials, supports such as polyethylene terephthalate are generally used.
It is easy to be charged especially in low humidity such as winter. In recent years, when high-speed photographic emulsions are applied at high speeds or when high-sensitivity photosensitive materials are exposed through automatic printers, antistatic measures are especially important.

When a photosensitive material is charged, static matter appears due to the discharge, or foreign matter such as dust is attached, which causes pinholes and deteriorates the quality significantly, making it extremely difficult to correct the problem. It will be. For this reason, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, and sulfone Polymers having acid or phosphoric acid groups in the molecule are used.

In particular, it has been widely used to adjust the charge series using fluorine-based surfactants, or to improve conductivity by using conductive polyamides.
No. 121523 discloses an example in which an ionic polymer having a dissociative group in the polymer main chain is applied.

However, in these conventional techniques, the antistatic ability is significantly deteriorated by the development process.

This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when a processed film is further used for printing, such as with printing photosensitive materials, problems such as pinholes occur due to adhesion of dust.

For this reason, for example, JP-A Nos. 55-84658 and 61-1
No. 74542 proposes an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine.

In this way, various methods have been proposed to improve antistatic performance, and although antistatic performance has improved, on the other hand,
As the film becomes thicker, sensitivity decreases and color retention deteriorates.

On the other hand, in recent years, rapid processing has become mainstream, and thinner films have become necessary. However, if the hydrophilic colloid layer other than the antistatic layer is made thinner, problems such as pressure fog in liquid due to high-speed conveyance and roller conveyance in automatic processors will increase, resulting in a significant deterioration of image quality. It's here.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which has improved antistatic performance without affecting photographic properties even in rapid development processing, and which has less pressure fog in the processing solution. The goal is to provide the following.

[Structure of the invention]

The above object of the present invention provides that on at least one side of the support,
In a silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer, at least one side of the support is charged with a reaction product of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (2) a hardening agent. A silver halide photographic light-sensitive material having an antistatic layer and containing a high boiling point solvent having a boiling point of 150° C. or higher in at least one layer of the antistatic layer, emulsion layer or other hydrophilic colloid layer. achieved.

The present invention will be explained in detail below.

The present invention is particularly effective in rapid processing based on recent demands as described above. In this case, rapid processing means a processing time of 20 to 60 seconds.

The water-soluble conductive polymer constituting the antistatic layer of the present invention may form a transparent layer even when used alone, or the layer may crack due to slight variations in drying conditions. The structure of the present invention contains hydrophobic polymer particles to prevent cracking, and the effect is significant.

The organic conductive polymer in the conductive layer used in the present invention has a molecular weight of 100 and has a sulfonic acid group or its base bonded to an aromatic ring or heterocyclic group directly or via a divalent linking group.
0 to 1 million, particularly preferably 1 to 500,000. The polymer can be easily synthesized by polymerizing monomers that are commercially available or obtained by conventional methods.

The conductivity of the conductive polymer of the present invention means that the specific resistance of the surface applied alone on a polyethylene terephthalate film of 2 g/m2 or more is 10100 (23℃ 12O%
RH).

Further, the organic conductive polymer used in the backing layer of the present invention can be selected from the organic conductive polymers contained in the conductive layer listed above.

The surface of the conductive layer of the present invention is preferably activated by corona discharge, glow discharge, ultraviolet rays, flame treatment, or the like. A particularly preferred activation treatment is a corona discharge treatment, which is preferably carried out at a rate of l mw −] kw/(m”m1n).A particularly preferred energy intensity is 0
．． The range is 1w −1w/(m2·m;n).

Further, it is preferable to provide an adhesive layer made of gelatin or a gelatin derivative on the conductive layer of the present invention, and these adhesive layers can be overlaid at the same time as the conductive layer is applied, or can be applied after drying.

This adhesive layer is preferably heat treated at a temperature range of 70°C to 200°C. Various hardening agents can be applied to this adhesive layer, but from the viewpoint of cross-linking between the lower conductive layer and the upper backing layer, acrylamide-based, aldehyde-based, aziridine-based, etc. Hardeners can be selected from peptide-based, epoxy-based, and hynylsulfone-based hardeners.

A conductive layer coating liquid mixed with a conductive polymer and latex is applied directly onto the support or after being coated onto the support. For the purpose of strengthening the conductive layer film, the crosslinking degree can be set to any desired degree.

However, in order to achieve the desired performance, the mixing ratio of the conductive polymer and latex, the coating and drying conditions of the conductive layer,
Since the selection of the crosslinking agent and the amount used etc. have an influence, it is preferable to set good conditions. By setting these conditions, a preferable degree of crosslinking of the conductive layer after coating and drying can be determined. The degree of crosslinking of the conductive layer due to the curing agent can be determined from the degree of swelling. The degree of swelling was determined by dipping the sample of the present invention into pure water at 25°C.
The sample was immersed for 0 minutes, and an adapter was attached to the sample to allow measurement of the swollen film thickness in water. The degree of swelling can be determined by observing with an electron microscope and comparing the film thickness when dry. The degree of swelling can be determined by the increase in film thickness due to swelling due to immersion/film thickness when dry. To indirectly determine the degree of swelling, calculate the amount of water absorbed from the weight of a sample of a certain area when dry and the weight of the sample when swollen, calculate the volume increased by this water, and calculate the specific gravity. The film thickness can be determined from the equation and used as the degree of swelling. Such a method can be applied to a backing protective layer, a backing layer, a silver halide emulsion layer, etc., instead of measuring the degree of swelling of a conductive layer.

The thickness of the conductive layer is closely related to conductivity, and as the characteristics improve with an increase in unit volume, it is better to make it thicker, but since the flexibility of the film will be impaired, it is better to make it thicker.
Good results can be obtained if the thickness is within 0.00μ, particularly preferably in the range of 0.1 to 10μ.

Next, specific examples of compounds of the water-soluble conductive polymer used in the conductive layer will be given.

H3 "10- CH2COOCH2CH20H H3 P -10 SO3Na H3 ■ 03Na 03Na 03Na =12- P -26 P -27 H3 M=lkaM"=800,000M Cape 30,000x:y:z2w=40:30 :2010M is also 500,000X:y・z=40:30:30 M is the mol% of the component, and M is the average molecular weight (
In this specification, average molecular weight refers to number average molecular weight).

It should be noted that the polymers most useful in the practice of this invention generally have an average molecular weight of about 10 million to about 100,000, as described above.

The amount of the conductive polymer contained in the conductive layer of the silver halide photographic light-sensitive material of the present invention is 0.0000000000000000000000000000000000,000,0000000000000000000000000000000,000,0000,000,000,000,000,000,000,000, It is preferable to add OO]g to ]Og, and particularly preferably to add 5g to 5g (LO).

When a water-soluble conductive polymer is used in a banking layer, backing protection or silver halide emulsion layer, it is preferable that the amount is 0.01 to ]Og in terms of solid content.

Next, let's talk about the curing agent used in the present invention.

As the curing agent used in the present invention, the following various curing agents can be used.

■Blocked isocyanate type ■Multifunctional aziridine type ■α-cyanoacrylate type ■Epoquin type containing triphenylphosphine ■Bifunctional ethylene oxide type and cured by electron beam or X-ray irradiation.

■N-Mediroll type ■Metal complex containing zinc and zirconium metals ■Silane coupling agent ■Carboxy activated type These hardening agents will be explained below.

(2) The blocked isocyanate curing agent used in the present invention is not particularly limited as long as it releases incyanate upon heating, but the compounds shown below are preferably used as specific examples.

■-2 0C2H5 0C21(5 NH-C-〇CH2CHC,H.

0 C21 (.

■-5 0C2H! ■-6 ■ C2Hs 〇-22= The above compound may be dissolved in water or an organic solvent such as alcohol or acetone and added as it is, or it may be added as it is, or it may be added as is, such as tothene rubensenesulfonate or nonylphenoquine alkylene oxide. It may be added after being dispersed using a surfactant such as. Preferably (2) The polyfunctional aziridine curing agent used in the present invention is represented by the following formula.

Here, R1 represents a hydrogen atom, an alkyl or aryl group having up to 20 carbon atoms, a hydroxy group, a halogen atom,
R2 represents a hydrogen atom or an alkyl group having up to IO carbon atoms.

The following are preferably used, but are not limited to these.

Next, the α-cyanoacrylate compound used in the present invention is represented by the following formula.

[In the formula, R represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. ] Specific examples will be shown below, but the invention is not limited thereto.

=26- (2) Next, the epoxy group-containing curing agent used in the present invention is not particularly limited, but as specific examples, the compounds shown below are preferably used.

Specific example compound ■ HH ,\1 C■.

=28- Most of the above compounds are commercially available and can be easily obtained. The addition method may be by dissolving it in water or an organic solvent such as alcohol or acetone and adding it as is, or by dispersing it using a surfactant such as dodenlebenzene sulfinate or nonylphenoquine alkylene oxide. It may be added from The preferred addition amount is 1 to 1.00
It is 0 mg/m2.

In addition, the effect can be further enhanced by using triphenylphosphine represented by the following formula together with the above-mentioned crosslinking agent.

[In the formula, R1 to R3 represent a substituted or unsubstituted argyl group, hydrogen atom, halogen atom, nitro group, cyan group, hydroxy group, or alkoxy group. ] Triphenylphosphine is not particularly limited, but as specific examples, the compounds shown below are preferably used.

4a-1 4a-2 CH.

H3 4a -3 0Next, the bifunctional ethylene ogicide compound used in the present invention is represented by the following formula.

CH2=CH-L-CH=CH2 [Wherein, L represents a substituted or unsubstituted alkylene oxide silver group. ] Specific examples will be shown below, but the invention is not limited thereto.

Concrete example CH.

5 3 CH2=CHC0(OCHzCH2)400
CCH= CH25-4CH2=CHC0(OCH2C
H2), 0OCCH=CH25-5CH3CH2C-(
CH200CCH=CH2)35-6 CI(3C
112C-(C)+20CH2CH200CC)l=c
l(2)3CH3CH3 CH=CH2(○CH2CH2)2300CG=CH2
CH2=CHC00(CH2CH20)3(CH=CH
2) 2-- (CH2CH20), 0CCH=CH2C
H3 ■ CH3CH2-(CH200CC=CH2)3 Conventionally, bifunctional ethylene oxide compounds were crosslinked by heating, but this method was slow in reaction and insufficient in crosslinking, resulting in low efficiency. The present invention is characterized by curing by electron beam or X-ray irradiation.

The intensities of electron beams and X-rays required for curing are as follows.

Electron beam intensity: 10-2-10'KW/m2 (50K
Particularly preferred is W/m2. ) X-ray intensity: 10-2-]06KW/m” (30
Particularly preferred is 0 KW/m2. ) Next, specific examples of the N-methylol compound used in the present invention will be shown, but the invention is not limited thereto.

6-1 6-2 CH20H Re0 Next, specific examples of metal complexes containing zinc and zirconium metals used in the present invention will be shown, but the present invention is not limited thereto.

Zn(NH3)acH3cOo)2Zn(NH3)tc
O3(NHJ3ZnOH(CO3)3) The amount of the metal complex used is preferably 10-3 to 103 moles per mole of the conductive polymer.

Conventionally, organic crosslinking agents have been mainly used, or crosslinking has become sufficient by using the metal complex of the present invention.

(2) In the present invention, a silane coupling agent can also be used as a curing agent as described below.

H2N CH2CH2N HCH2CH2CH2S l
(OCH3) 3CH2=CH5i (OCH+)3 and other silane coupling agents (2) Scarfoxyl group-activated curing agents are also used in the present invention. For example, the following carbodiimide type curing agents are used.

'll-1 Next, the hydrophobic polymer particles according to the present invention will be explained.

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are contained in a so-called latex form that is substantially insoluble in water. This hydrophobic polymer contains monomers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. Obtained by polymerization. Especially styrene derivatives, alkyl acrylates,
Preferably, the alkyl methacrylate content is at least 30 mol %. Particularly preferred is 50 mol% or more.

There are two methods to make a latex from a hydrophobic polymer: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent and finely dispersing it, followed by distilling off the solvent. Emulsion polymerization is preferable because it allows the production of

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
It is preferably 0% by weight or less. A large amount of surfactant causes clouding of the conductive layer.

The molecular weight of the hydrophobic polymer may be 3000 or more,
There is almost no difference in transparency depending on molecular weight.

Specific examples of the hydrophobic polymer of the present invention will be given below.

Specific examples of hydrophobic polymer particles One old one =40- a CH3 tsu ■ CQ CH.

L-3 L-9 M-150,000 In the present invention, a high boiling point solvent means an inorganic/organic ratio [see "Organic Conceptual Diagram" (written by Yoshio Koda, Sankyo Publishing Co., Ltd.]) of less than 0.07, preferably indicates a compound having a boiling point of 150°C or more, preferably 200'C! The organic solvent is liquid at a melting point of less than 130°C, preferably less than 80°C, and particularly preferably at room temperature (25°C).

Examples of high boiling point solvents that can be used in the present invention include U.S. Pat.
No. 14, No. 2,835,579, No. 3.287.
No. 1.34, No. 2,353゜262, No. 2.85
2.383, 3,554,755, 3,6
No. 76.137, No. 3,676.142, No. 3,
No. 700.454, No. 3,748.141, No. 3
, 779, 765, same number 3゜837.863,
British Patent No. 958.441, British Patent No. 1. ．． 222,75
No. 3, ○L No. 32,538.889, JP-A-1973-1
No. 031, No. 49-90523, No. 50-23823
No. 51-26037, No. 51-27921, No. 51-27922, No. 51-26035, No. 5],
-26036, 50-62632, 53-15
No. 20, No. 53-1521, No. 53-1.51.27
No. 54-11.9921, No. 54-11.992
No. 2, No. 55-25057, No. 55-36869,
It is described in No. 56-19049, No. 56-81836, and Japanese Patent Publication No. 48-29060.

The high boiling point solvents preferably used in the present invention are those shown below.

General formula [A] Issatsu CB] =44= General formula [C] General formula [D] Issatsu CE'1 In formulas (A) to (E), R, R,, R2 and R3 are each a hydrogen atom, A straight chain, cyclic or branched alkyl group, preferably a straight chain, cyclic or branched alkyl group having 1 to 30 carbon atoms (for example, a methyl group, ethyl group, propyl group, l-propyl group, butyl group, cyclohexyl group) , t-
butyl group, amyl group, hequinyl group, decyl group, dodecyl group, hexadecyl group, etc.), alkoxy group, preferably alkoxy group having 1-45 to 30 carbon atoms (e.g. methoxy group, ethoxy group, 1-propoxy group, t-butoxy group, etc.), aromatic group,
Preferably an aromatic group having 6 to 30 carbon atoms (e.g. phenyl group, naphthyl group, etc.) or a heterocyclic group, preferably a heterocyclic group having 4 to 30 carbon atoms (e.g. furyl group, thio7lyl group) , pyrazolyl group, oxazoyl group, pyridyl group, piperazyl group, indolyl group, quinolinyl group, etc.).

The linear, cyclic or branched alkyl groups and alkoxy groups represented by R, R+, R2 and R3 include those with substituents, such as aromatic groups (e.g. phenyl group, p-methoxyphenyl group). , 2.4-Ct-amyl phenyl group, etc.), carbonyl group (e.g. acetyl group,
benzoyl group, etc.), amino group (e.g., anilino group, etc.),
Alkoxy group (e.g. methoxy group, ethoxy group, etc.),
Examples include aryloxy groups (for example, 2,4-di-amylphenoquine groups, etc.), heterocyclic groups (for example, furyl groups, etc.), cyano groups/%rogen atoms (for example, fluorine atoms, chlorine atoms, etc.).

-4[i- The aromatic groups represented by R, R,, R2 and R3 include those having substituents, and examples of substituents include alkyl groups (for example, methyl group, L-butyl group, L- amyl group, etc.), alkokene groups (e.g., methoxy group, ethquine group, etc.), carbonyl groups (e.g., methoxycarbonyl group, etc.), and halogen atoms (e.g., fluorine atom, chlorine atom, etc.).

The heterocyclic groups represented by R, R,, R2 and R3 include those having substituents, such as alkyl groups (for example, methyl group, ethyl group, L-butyl group, etc.), aromatic group groups (e.g., phenyl group, ), lyl group, etc.), alkoxy groups (e.g., methoxy group, xyl group, etc.), carbonyl groups (e.g., tomexycarbonyl group, etc.), halogen atoms (
Examples include fluorine atoms, chlorine atoms, etc.). however,
In the formula, when R is a bond between two residues, R is a simple bond, a linear, cyclic or branched alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, 1-butylene group, octylene group, tetradecamylene group, /chlorohexylene group), alkenylene group (for example, hynylene group, 2-j thenylene group, propenylene group, cyclohexenylene group), alkynylene group (
Examples include ethynylene group), and arylene groups having 6 to 30 carbon atoms (eg, phenylene group, naphthylene group, anthrylene group). If R is a bond between 3 or more residues, use 〉C-C.

Further, when R, R, , R2 and R3 have a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of R, R, , R2 and R3.

+2. m and n represent integers of 0 to 6, and at least one in the same molecule represents an integer of 1 to 6. RlR,,R2
and R3 may be the same or different.

Any two of R, R+, R2 and R3 may be combined to form a 5- to 7-membered ring.

Specific examples of the high boiling point solvent of the present invention are shown below, but the invention is not limited thereto.

-Specific examples corresponding to brutality [A] ?・H・ 149= CH+ nH.

2H5 2H5 a-8 &-13 Specific example corresponding to general formula CB) H ■ CH3-CH-C0○-CI2H25 ■ CH2C00C7H15 (iso) CH20COCIIH23 HC-OCOC,,H23 CH20COCI IH23 -Next door- b-6 C,,H,,C00CH3 -g C2H.

CH2-COOCH2CH-Cd(.

2H5 2H5 2H5 2H5 ■ CH2 COOCH2CH C4H9(CH2)6 CH2 COOCH2CH CtHs2H5 Specific example c- corresponding to general formula [C] m5 m5 m7 cm9 1', 0-- Specific example 14i corresponding to general formula CD) :l- d -10 d-11 =63- Specific example corresponding to general formula [E] In the present invention, two or more types of high boiling point solvents (hereinafter abbreviated as HBS) may be used in combination. In this case, it is also possible to combine HBS, which is liquid at room temperature, and HBS, which is solid at room temperature.The amount of HBS applied per interlayer-layer is 0.00.
1g/m2-5.0g/m2, preferably 0.05-
3.0 g/m2.

Methods for adding HBS include a method in which it is dissolved in a water-miscible solvent such as methanol, acetone, dimethylformamide, etc., and a method in which it is added as an aqueous dispersion using a ball mill, a sand mill, an ultrasonic dispersion machine, etc. HBS
Other photographic additives may coexist in the dispersed particles, or it is preferable that no other photographic additives coexist in order to further enhance the effects of the present invention. The additive may be added to the hydrophilic colloid layer constituting the light-sensitive material, or preferably in the emulsion layer.

The term "hydrophilic colloid layer" as used in the present invention refers to a hydrophilic layer provided on a silver halide photographic light-sensitive material, such as a silver halide emulsion layer, a protective layer, an intermediate layer containing a binder component such as gelatin, etc. Refers to various layers necessary for photographic light-sensitive materials, such as layers, anti-rayon layers, filter layers, development control layers, ultraviolet absorbing layers, undercoating layers, and printing layers.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be a silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, etc., but it is said that particularly high sensitivity can be obtained. From this point of view, silver iodobromide is preferable.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may be a completely isotropic crystal like a tetrahedron, a polyhedral crystal like a sphere, a twin crystal with planar defects, or a mixed or composite type thereof. The grain size of these silver halogen grains is 0.1
The particles may be fine particles of .mu.m or less to large particles of 20 .mu.m.

The emulsion used in the silver halide photographic material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (197
(December 2008)・Pages 22-23 1・Emulsion manufacturing method (Emu
lsionPreparation and type
es) and the same (RD) No. 187]6 (197
It can be prepared by the method described on page 648 (November 1999).

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described, for example, in "The theory o" by T. H. James.
f thephotograph ic processes
s” 4th edition, published by Macm Hyakufan (1977) 38
- The method described on page 104, by G. F. Dauffin, “
"Photographic emu chemistry""Photographicemu"
lsionChemistry”, Focal pr
Published by ess (1,966), P. Glafkides
Author: “Physics and Chemistry of Photography” by Chimie etphysi
Paul M
Published by onte1 (1967), V, L, Zelik
Author: ma6 et al. [Manufacturing and Coating of Photographic Emulsion J ”Makin
g and coating, photography
cemulsion” Published by Focal press (
(1964) and others.

That is, solution conditions such as neutral method, acidic method, and ammonia method,
It can be produced using mixing conditions such as forward mixing method, back mixing method, double jet method, Chondral double jet method, etc., particle preparation conditions such as conversion method, core/shell method, and combination methods thereof.

A preferred embodiment of the present invention is a monodispersed emulsion in which silver iodide is localized inside the grains.

A monodisperse emulsion as used herein means that when the average particle diameter is measured by a conventional method, at least 95% of the particles in terms of number or weight are within ±40% of the average particle diameter, preferably within ±30%. It is a certain silver norogenide grain. The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The crystal structure of silver halide may have different silver halide compositions inside and outside.

The emulsion as a preferred embodiment of the present invention is a core/shell type monodisperse emulsion having a clear two-layer structure consisting of a high iodine core portion and a low iodine shell layer.

The silver iodide content of the high iodide portion of the present invention is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

=69- The manufacturing method of such a monodisperse emulsion is known, for example, J, Ph.
ot, Sic, 12°242-251 (1963)
, JP 48-36890, JP 5246364, JP 55-142329, JP 58-49938, British Patent No. 1,413,748, U.S. Patent No. 3, 574, 62
No. 8 and No. 3,655,394.

The monodispersed emulsion mentioned above is particularly preferably an emulsion in which grains are grown by using seed crystals and supplying silver ions and halide ions using the seed crystals as growth nuclei. In addition,
Methods for obtaining core/shell emulsions are detailed in publications such as British Patent No. 1,027.146, U.S. Patent No. 3,505,068, U.S. Pat. It has been stated.

The silver halide emulsion used in the present invention may be tabular grains having an aspect ratio of 5 or less.

The advantages of such tabular grains include improved spectral sensitization efficiency and improved image granularity and sharpness, as described in British Patent No. 2,112,1.57 and U.S. Patent No. 4,43, for example.
No. 9,520, No. 4,433,048, No. 4,414
, No. 310 and No. 4,434,226.

The emulsion mentioned above may be a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. good. In these emulsions, cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be used in the stage of physical ripening or grain preparation. The emulsion may be washed with water to remove soluble salts, such as the Tardel water washing method, the 70 mL precipitation method, or the ultrafiltration method. As a preferable water washing method, for example, Japanese Patent Publication No. 35-16086
Particularly preferred desalting methods include a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group as described in JP-A-63-158644, or a method using an example of an aggregating polymer agent such as c 3 or c B described in JP-A-63-158644. It will be done.

Various photographic additives can be used in the emulsion according to the present invention in the steps before and after physical ripening or chemical ripening. Examples of known additives include compounds described in Research Disclosure No. 47643 (December 1978) and Research Disclosure No. 18716 (November 1979). Compound types shown in these two research disclosures and =71- Additive RD-17643RD-18
Page 716 Classification Page Classification Chemical Sensitizer 23III648-Upper Right Sensitizing Dye 23rV648 Right-649
Left development accelerator 29 XXI 648-Right upper blade blur prevention agent 24VI649-Right lower stabilizer // 11 Color stain prevention agent 25 ■ 650 Left-Right image stabilizer 2
5 ■ Ultraviolet absorber 25-26 ■ 649 right-650 left filter dye // // Brightener 24 V hard
Coating agent 26X65] Left coating aid 26-27 n 650 Right surfactant 26-27 XI 650 Right plastic
Agent 27 Xll tt Slip agent l/Static inhibitor 27 ff ノ! mat
Agent 28
-18716, page 647, left column.

Suitable supports include plastic films, and the surfaces of these supports may generally be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve adhesion of the coating layer. Then, the emulsion according to the present invention can be coated on one or both sides of the support thus treated.

The present invention is applicable to all silver halide photographic materials, but is particularly suitable for high-sensitivity black-and-white photographic materials.

When applying the present invention to medical X-ray radiography,
For example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light when exposed to penetrating radiation is used. It is preferable to expose this material in close contact with both surfaces of a light-sensitive material prepared by coating both surfaces with the emulsion of the present invention.

The penetrating radiation referred to here refers to high-energy −,,7
, 1- Electromagnetic waves, meaning X-rays and comma-rays.

Further, a fluorescent intensifying screen is, for example, an intensifying screen whose fluorescent component is mainly calcium tungstate, or a screen whose main component is a rare earth compound activated with terbium [Example] The following is an example of the present invention. I will explain about it. However, it goes without saying that the present invention is not limited to the examples described below.

Example 1 Reaction vessel conditions: 60°C, pAg=8, and pH
-2 while maintaining the average particle size of 0.
A monodisperse cubic emulsion of silver iodobromide containing 2 mol % of silver iodide of 3+1 m was obtained. According to electron microscopy, the incidence of twins was less than 1% in number.

Using this emulsion as a seed crystal, the crystals were further grown as follows.

The seed crystals were dissolved in an aqueous gelatin solution kept at 40° C. in a reaction vessel, and aqueous ammonia and acetic acid were added to adjust the pH to 9.5.

After adjusting pAg to 7.3 with ammoniacal silver ion solution,
While keeping the pH and p/1g constant, a solution containing ammoniacal silver ions, potassium iodide and potassium bromide is added using a double jet method to form a silver iodobromide layer containing 30 mol% of silver iodide. I forced it.

After adjusting the pH to 9 and pAg to 9.0 using acetic acid and silver bromide, an ammoniacal silver ion solution and potassium bromide were added at the same time, and the particles were grown until they reached 90% of the grown particle size. At this time, the pH was gradually lowered from 9o to 8.2o.

After adding potassium bromide solution to make pAg-II, ammoniacal silver ion solution and thulium bromide were further added to grow while gradually lowering the pH to 8, resulting in an average particle size of 0.7μ.
A silver iodobromide emulsion containing 2 mol % of silver iodide was obtained.

The obtained emulsion was kept at 40°C, and a formalin resin of 7-talene sulfonate (average degree of polymerization 4 to 6) was added to the emulsion.
) to precipitate the silver halide grains, drain the supernatant, add 40'O pure water, add magnesium sulfate, precipitate the silver halide grains again, and drain the supernatant. The liquid was removed.

-7[i- After changing this again, gelatin was added and pH=
6.0. An emulsion with pAg=8.5 was obtained.

Ammonium thiocyanate chloroauric acid and Hypo were added to the resulting emulsion, and chemical ripening was performed under conditions that yielded the highest sensitivity.

Then 4-hydroxy-6-methyl-1- as a stabilizer
An appropriate amount of 3,3a,7-chitrazaindene was added to obtain an emulsion.

In addition, when chemically sensitizing the emulsion, the following sensitizing dye (A) was added at 300 mg per mole of silver in the emulsion, and the sensitizing dye (B) was added at 15 mg per mole of silver in the emulsion.
mg was added.

To the obtained emulsion were added the emulsion and additives described later in the proportions shown in Table 1 and a high boiling point organic solvent preparation solution described later to prepare an emulsion coating solution.

Spectral sensitizing dye (A) Spectral sensitizing dye (B) (Emulsion coating solution) The additives used in the emulsion coating solution (photosensitive silver halide coating solution) are as follows. The amount added is expressed per mole of silver halide.

L-butyl-catechol 400mg
Polyhinylpyrrolidone (molecules! 10,000) ],
]Og Styrene-Maleic Anhydride Copolymer 2.5g Trinotyrolpropane 10g Diethylene Glycol 5g2L・Lophenyltriphenyl=78- Phosphonium Chloride 50mg1,
Ammonium 3-dihydroxybenzene-4-sulfonate 4g2-Mercaptobenzimidanol-5-sulfonate I.lium 1.5mg
1-7enyl-5-mercaptotetrasol 1m (
HH (Protective layer liquid) The additives used in the protective layer liquid are as follows. The amount added is expressed per celadin Ig.

Matting agent made of polymethyl methacrylate with silicon dioxide particles having an area average particle size of 7 μm 7 mg Colloidal silica (average particle size of 0.013 μ”) 70 mg
2.4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30m
g(CH2=CH3O2-CH$0
36 mg 03Na = 79- Note that, as shown in Table 1, a high boiling point solvent dispersion according to the present invention prepared as described below was added to the protective layer and the emulsion layer.

(Preparation of high-boiling organic solvent dispersion) A solution of the high-boiling organic solvent logs of the exemplary compounds shown in Table 1 mixed with ethyl acetate was added to a 5% aqueous gelatin solution containing a surfactant, and dispersed with an ultrasonic homogenizer. It was prepared by distilling off ethyl acetate and adding a small amount of water.

The following supports were prepared and used as supports according to the present invention.

After corona discharge with an energy of 8 W/m2-m1n onto a 180 μm blue-colored polyethylene terephthalate base subbed-treated, an antistatic liquid having the following composition was applied.
Coating was carried out using a roll-fit coating pan and an air knife at a speed of 30 m/min so that the coating amount was as shown below.

s6 (Antistatic layer) Water-soluble conductive polymer Hydrophobic polymer particles shown in Table-1 Curing agent shown in Table-1 Furthermore, this antistatic layer was subjected to the above-mentioned corona discharge treatment as a surface activation treatment. provided.

Next, each of the obtained emulsion and protective layer coating solutions was uniformly coated on the antistatic layers on both sides of the support and dried to prepare Samples 1 to 18 shown in Table 1.

The amount of coating was adjusted for all samples so that the amount of gelatin on both sides was as shown in Table 1, and the amount of silver was 4.6 g/m2.

(Centometry evaluation) The obtained sample was sandwiched between X-ray photographic intensifying screens KO-250 (manufactured by Konica Kano), and passed through a penetrometer (manufactured by Konica Medical Kanko) after X-ray irradiation. Using an automatic processor, the samples were processed with an XD-5R developer (both manufactured by Konica Kai) while changing the processing time. Here, the processing time is the time required to complete all steps from development to drying.

=82- Sensitivity was expressed as a relative sensitivity based on the reciprocal of the amount of light necessary for the blackening density to increase by 1.0 above the fog, and with the sensitivity of sample No. 091 set as 100.

(Evaluation of in-liquid blemish fog) Samples were cut into 127 x 305 mm, and pre-exposed and unexposed samples were measured so that the density after development was approximately 1°0.0.6.0.4. Two types of samples were prepared.

The exposed and unexposed samples were processed in the same manner as above, with varying processing times.

The appearance of black spots on exposed and non-exposed samples was examined and evaluated in 5 grades depending on the appearance of black spots.

◎: Not generated at all O: Slightly generated △: Occurs, but lower limit of practical use Interval 0.14cm, length 10cI1
Insulation meter TR865 made by Takeda Riken was inserted between the electrodes made by No. 1 made by Masuzu.
Measurement was performed for 1 minute using Type 1. Samples were used before and after development, each at a temperature of 25°O and a RH of 20%.
After adjusting the humidity for 2 hours, measurements were taken.

8ri - As shown in Table 1, the samples of the present invention have high sensitivity in rapid processing, excellent surface conductivity, and excellent surface conductivity.
It can be seen that the fog resistance is also excellent. In particular, it can be seen that the sample with a thinner film for rapid processing has excellent resistance to submerged spraying.

Example 2 KBrlOg, thioether (HO(CH2)
Q of 2S(CH3)2S(CH2)20H), 5wt%
, gelatin 30g 1 water 10m0. Add and dissolve at 70℃
I kept it. In this solution, AgNO3 aqueous solution 0.88 mol/Q 30 mQ, Kl and KBr (molar ratio 3.5°96
．． 88 mol/(230 mff) of the aqueous solution layer of 5) was added by the tuple jet method. After the addition of the mixture was completed, the mixture was heated at 40°C.
The temperature was lowered to 6.0.

Thereafter, desalting and chemical sensitization were performed in the same manner as in Example 1 to obtain an emulsion.

Using this emulsion, samples according to the present invention as shown in Table 2 were prepared. The coating structure and various additive conditions were all the same as in Example 1.

The results obtained are shown in Table 2 below.

From the results in Table 2, it can be seen that the samples of the present invention have high sensitivity even in rapid processing, as well as good antistatic performance and in-liquid pressure resistance.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material that has high sensitivity even in rapid processing, good antistatic performance, and in-liquid printing and printing resistance.

Claims (1)

[Claims] In a silver halide photographic material having a photosensitive silver halide emulsion layer on at least one side of a support, on at least one side of the support (1) a water-soluble conductive polymer, (2) a hydrophobic polymer, (3) has an antistatic layer made of a reaction product of a curing agent, and at least one of the antistatic layer, emulsion layer, or other hydrophilic colloid layer has a boiling point of 150°C or higher; A silver halide photographic material characterized by containing a solvent.