JPS5856860B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material that prevents charging failures such as static mark failures without adversely affecting photographic properties.

More specifically, there is no deterioration in antistatic performance even if rapid drying is performed in the drying process during manufacturing and processing of silver halide photographic materials, and antistatic agents etc. are precipitated in the processing solution during the processing process. The present invention relates to a silver halide photographic material that does not deteriorate in image quality due to roughness of developed silver particles that occurs during processing steps.

It is known that plastic films used in photographic materials are easily charged due to friction or peeling, and can cause various problems such as dust attraction, electric shock, and ignition.

For example, in the case of silver halide photographic materials that use plastic films as supports, there are various steps during their production, including winding, rewinding, coating of various coating layers including photosensitive layers, and drying. During transportation and other processes, the material becomes charged due to friction or peeling from other substances, and when this discharges, the photographic material coated with the photosensitive layer is exposed to light, and after development, an undesired image called a static mark is formed. This causes uneven exposure due to regular static electricity.

Furthermore, when using or processing manufactured photosensitive materials, if static electricity is charged, especially under conditions of low humidity, static mark failures may occur as well, and various problems may occur due to the adhesion of dust, etc. resulting in disability.

The more sensitive the photosensitive material is, the more this static mark occurs, but in addition to the recent advances in the sensitivity of photosensitive materials, there has been an increase in the number of opportunities for them to be subjected to harsh mechanical handling due to high-speed automatic processing. There is a tendency for this to occur more frequently.

Conventionally, various substances have been used as antistatic agents for plastic films in general, but in the case of silver halide photographic materials that use plastic films as a support, in addition to preventing static mark failure, the following It is required to have various characteristics such as:

In other words, in addition to having excellent antistatic properties, the material must not have a negative effect on the photographic properties of the photographic light-sensitive material, such as its sensitivity, gradation, fogging, and storage stability, and must not be bonded to other materials or to other materials. There should be no adhesion or transfer phenomena when using the product, good adhesion to adhesive tapes, etc., no problems due to bleed-out phenomenon, and there should be no problem in processing liquids during processing steps such as development, fixing, and water washing. It is required that the treatment solution not be precipitated or clouded.

In addition, in general, when silver halide photographic materials are rapidly dried during the drying process, the crystalline arrangement of the binder such as gelatin and the orientation of the antistatic agent are disrupted, resulting in deterioration of the antistatic performance. Measures are required to

In addition, in the course of research, it was newly discovered that among antistatic agents, nonionic ethylene oxide compounds have the effect of roughening developed silver particles after processing when used in large quantities, causing deterioration of image quality.

At present, it is not clear whether this is due to the effects of these compounds themselves or whether these compounds occur because they deteriorate the physical properties of the gelatin film.

This is a completely undesirable property in terms of product quality in photographic films, and is a problem that must be overcome when using these compounds as antistatic agents.

As mentioned above, antistatic techniques for silver halide photographic materials require special techniques that are not required for antistatic techniques for plastic films in general.

That is, in order to satisfy the above properties, it is desired to find an excellent antistatic agent and/or to develop an auxiliary agent that can keep the amount of antistatic agent used to the minimum necessary.

A first object of the present invention is to provide a silver halide photographic light-sensitive material that does not adversely affect photographic properties and is free from charging failures such as static mark failures.

The second object of the present invention is to (1) reduce the precipitation of the antistatic agent in the processing solution as much as possible, and virtually eliminate malfunctions caused by this, by keeping the amount of antistatic agent used to the minimum necessary. , 2) Eliminates deterioration in image quality due to roughening of the developer caused by antistatic agents, and 3) Silver halide photographic sensitization that makes it possible to avoid adhesion between photographic light-sensitive materials or with other substances. The goal is to provide materials.

It is an object of the present invention to provide a hydrophilic constituent layer of a silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (1) or [hence] and an average molecular weight of
This can be achieved by using a silver halide photographic light-sensitive material containing at least one of the following.

General formula L÷CH2CH2O+mH General formula General formula [D and [] where R is a substituted or unsubstituted alkyl group (preferably 1 to 22 carbon atoms)
), alkenyl group or ary group, L is 101 group, -
81 group, N R/ group (wherein R' group represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 22 carbon atoms), or a moCH2CH2O+r11H group.

same as below. ), -C-N-R' group or -C-O- group,
R, and II+ 110 R2 are hydrogen atoms, halogen atoms, carboxyl groups, acyl groups, alkoxycarbonyl groups, substituted or unsubstituted alkyl groups (preferably having 1 to 22 carbon atoms), alkoxy groups, alkenyl groups (preferably has 1 to 2 carbon atoms
2), acetoxy group, nitro group or phenyl group, R
3 represents a hydrogen atom, a methyl group or an α-furyl group,
m and n represent integers from 2 to 50.

General formula (II) + A + - + B + b In the formula, A is vinyl alcohol, acrylic acid, methacrylic acid, maleic acid, itaconic acid, carboxystyrene, vinyl sulfonic acid, sulfostyrene and alkali metal salts thereof, and It represents a monomer derived from vinyl hydrolidone, vinyl oxazuduridinone, and a vinyl compound having the following side chain (M represents an alkali metal atom).

B represents a monomer other than A that can be copolymerized with A, and a is 3
0 to 1OO mol%, and b represents 70 to 0 mol%.

Examples of the monomer represented by B in general formula (1) include styrene, 0-methylstyrene, m-methylstyrene, P-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-methylstyrene, -n-butylstyrene, p-tert "methylstyrene, p-
n-hexylstyrene, p-'-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene,
Styrenes such as p-n dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene; ethylenically unsaturated monoolefins such as vinylnaphthalenes, ethylene, flopylene, butylene, and isobutylene; , vinyl esters such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl flopionate, vinyl benzoate, vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Propyl, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, methacrylate Ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, methacrylic acid 2
- α- of ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.
Examples include methylene aliphatic monocarboxylic acid esters, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

That is, the present inventor has proposed that a polymer having an average molecular weight of 106 or less represented by the general formula (IID) be added to the hydrophilic colloid layer of a silver halide photographic light-sensitive material together with at least one compound represented by the general gD and [silver]. (hereinafter simply "general formula (I
It has been found that the above object can be achieved by containing at least one type of polymer II).

According to the research of the present inventors, the above general formula (1) and (
If one of the compounds represented by ID is used in combination with the polymer of general formula (III), an extremely superior antistatic effect will be exhibited than when only the compounds represented by general formulas [I] and [formula] are used. It turns out.

Furthermore, the amount of the antistatic agent, which is a compound represented by general formulas [I] and (II), can be kept to the minimum necessary by using it in combination with the polymer of general formula (1). Adhesion phenomenon between photographic materials or other substances (so-called stickiness phenomenon) caused by the use of large amounts of inhibitors
It has been found that it can prevent this and improve the adhesion with adhesive tapes, etc., and can serve a distant relative of the above-ground purposes.

The compounds represented by the general formula CI) used in the present invention include those shown by the following general formula.

[General formula]

CI)-(A) R-OmoCH2CH2O+mHm-2~50R is an alkyl group and may have an unsaturated bond, preferably having 4 carbon atoms
-22, hydrogen may be substituted with fluorine.

(1)-(B) R,, R2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a carboxyl group, an acyl group, an alkoxycarbonyl group, an alkyl group, a substituted alkyl group,
Represents an alkoxy group or a phenyl group.

Hydrogen may be substituted with fluorine.

[D (0 R-8-fCH2CH20+mHm=2-50R is an alkyl group that may have an unsaturated bond, preferably has 4 to 22 carbon atoms, and hydrogen may be substituted with fluorine.

CI')-(1m/R2 1"-\CH2CH2O+,, H m=2~50 R1 is an alkyl group, preferably one with 1 to 20 carbon atoms, R2 is a hydrogen atom, an alkyl group (with 1 to 20 carbon atoms) ), fluorine-substituted alkyl group, phenyl group, alkyl-substituted phenyl group or +CH2CH2O+mH group.

Q)-(E) /R・R,C-N\('CH2CH2O+,, H1 m=2-50 R1 is an alkyl group, preferably one with 1 to 20 carbon atoms, R2 is a hydrogen atom, 1 to 20 carbon atoms), a fluorine-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a +CH2CH2O+mH group.

[:IE-(F5 RC-0 CH2CH2O+mHm=2-501 R1 represents an alkyl group, preferably one having 4 to 22 carbon atoms.

Among these compounds represented by the general formula [D], particularly preferred compounds in the present invention include the following.

[Exemplary compounds]

(1)-(1) C5H,, □0 to C12H25,H (r)-(2) Cs HIT O+ CH2CH20+ to H(
1)-(3) C12H25-O-f-CH2CH20+9H general KI
The compounds represented by ) or [formerly are generally known as antistatic agents in the art, but in order to have a sufficient antistatic effect, it is necessary to use a large amount.

However, in this case, the antistatic agent may precipitate in the processing solution and generate sludge, deteriorate the adhesion with the adhesive tape, cause adhesion between photographic materials or other substances, or cause the developed silver to deteriorate. It has the property of deteriorating image quality and causing various malfunctions.

Therefore, it is desirable to use the antistatic agent in as small an amount as possible, and an auxiliary agent is required that allows the antistatic agent to exhibit its antistatic effect within the upper limit of the allowable addition amount that does not cause the above-mentioned failure.

The object of the present invention is to synthesize a polymer of the general formula (III) with a polymer of the general formula [I
] or [It was achieved by using it in combination with the compound shown in the ship. First, let's talk about the antistatic effect. The polymer of general formula (III) alone has no antistatic effect in low humidity. It is completely insufficient and cannot be called an antistatic agent.

On the other hand, the compound represented by the general formula [D or [岨] will not be effective unless added in such a large amount as to cause the various failures described above.

However, the present inventors found that when the polymer of general formula [Machi] is used in combination with the compound represented by general formula (1) or [ It has been found that even when used in a small amount, sufficient effects can be exerted even in low humidity.

Although the mechanism of this effect has not yet been elucidated in detail, conventional techniques using only the general formula [0 or (9)] require the use of large amounts of these compounds in order to achieve sufficient antistatic effect. , the antistatic agent may flow out of the film and precipitate during processing, the photosensitive materials may adhere to each other or other substances, the developed silver may become rough and the image quality may deteriorate, the antistatic agent may come into contact with the photosensitive material, etc. It is impossible to avoid failures such as transfer to other materials and staining them.

These failures can be sufficiently eliminated in practice by reducing the amount of antistatic agent used.

In the present invention, by using the polymer of the general formula [■] in combination with the compound represented by the general formula (1) or [old],
The amount of the former compound used can be reduced.

In this case, by adjusting the amount of the polymer of the general formula [■] used, compared to the case where only the compound shown by the general formula mark or [river] is used in the conventional technology, the amount of the polymer of the general formula CI
) or [■] can be used in approximately 3/4 to 1/3 of the amount used in the prior art.

This unexpected effect is revolutionary in terms of antistatic technology for photosensitive materials.

In JP-A No. 54-89626, a polyol compound is used in place of the polymer of the general formula [■] of the present invention, but the present invention allows a greater reduction in the amount of antistatic agent used; Furthermore, polyols have the disadvantage that if used in too large an amount, they may cause stickiness between the films, but the polymer of the general formula (III) of the present invention does not have this problem and is technically superior.

Further, the above-mentioned document describes that polyvinyl alcohol, polyvinyl pyrodone, etc. included in the general formula (110) of the present invention can be used together with the compound represented by the general formula [0 or [R] of the present invention, The present invention is based on the discovery that the objects of the present invention can be significantly achieved by using a polymer having an average molecular weight of 106 or less.

The compounds represented by the above general formulas used in the present invention can be easily achieved by known methods.

Next, I will list the literature describing the synthesis method.

For example, the compound represented by General Zhao 1] is as follows.

[0-A Hiroshi Susuguchi "New Surfactant" 615-631 (1975) CD-B Hiroshi Susuguchi "New Surfactant" 644-670 (1975) [0-C Hiroshi Susuguchi "New Surfactant" 642-644 (1975) Seal-D Hiroshi Susoguchi "New surfactant" 638-642 (1975) (I)-E Hiroshi Susoguchi "New surfactant" 638
(1975) [0-F Hiroshi Susuguchi "New Surfactants" 631-638 (1975) General formula [Many of the compounds contained in D are commercially available as nonionic surfactants, and are easily available. It is something.

In addition, the compound represented by the general formula (9) is "Industrial Chemistry Magazine", Vol. 66, 391 (1963), "Oil Chemistry", Vol. 12, 625.
(1963) and Japanese Patent No. 279014, etc., but may be synthesized by other methods.

Further, the polymer of the general formula (III, 1) is W, R, 5ore
uson.

Preparative Methods of Polymer Chemistry, co-authored by T., W. and Campbell.
(John Wi)
ley & 5ons, Inc.

New York 1961) and Lanie Schuliednicht (C,E, 5childknecht)
) Written by Vinyl & Related Polymers (V
inyl and Re1ated Polymers
) (John Wiley & 5ans, Inc.
New York (1952), etc., various polymerization reactions and conditions such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be arbitrarily adopted for synthesis.

At least one compound represented by the above general formula CI) or [Haki] used in the present invention and at least one polymer of the above general formula [Haki] are combined into a hydrophilic colloid constituting a silver halide photographic light-sensitive material. The intended purpose can be achieved by incorporating it into the layer.

The hydrophilic colloid layer containing the above substance of the present invention may be any layer such as a silver halide emulsion layer, a subbing layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, a backing layer, etc. .

Further, it is effective to contain the compound represented by the general formula [D or [button] and the polymer of the general formula (III'l) in the protective layer or surface layer, but they may be contained in other layers.

In order to incorporate the substance, it is dissolved in water or a solvent compatible with water (for example, lower alcohols, esters, ketones) or a mixed solvent thereof in the coating solution for forming the hydrophilic colloid layer. Just add it.

The addition time may be at the time of application or any time before application, but
When the layer to be contained is a silver halide emulsion layer, it is preferably added after chemical ripening and during coating.

The amount of the substance used in the present invention is expressed by the general formula [I].

[When the compound represented by the fence is combined with the polymer of general formula (III)] and applied to a silver halide photographic light-sensitive material,
The amount varies depending on the type of each substance, the location to which it is applied, and the drying conditions after application, but the general formula (1)
, CI may be present in an amount of about 0.0025 to 5 g per square meter of the photosensitive material, but generally, per square meter,
About 0.01 to 0.5 g is sufficient.

In addition, for the polymer of the general formula (IID), the relaxation is preferably in the range of 1 to 800, and preferably from 1 to 800, per 1 g of gelatin contained in the layer, whether used alone or in combination of two or more. More favorable results are obtained in the range of 4400 mI?

However, it goes without saying that the above usage amount is appropriately selected depending on the type of silver halide, the layer or compound to be added, and the like.

The compound represented by the general formula (1) and/or the general formula according to the present invention [the compound represented by the former and the general formula ([[l]
These polymers may be mixed in advance and then added to the coating solution, or they may be added to different layers since there is no difference in effect even if they are added separately.

Various hydrophilic colloids including gelatin are used as binders for the silver halide photographic material of the present invention.

In this case, gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and isocyanate, or a compound having gelatin and an active halogen atom. This includes reaction products with and the like.

Examples of acid anhydrides used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and phosphoric anhydride; examples of incyanate compounds include , such as phenyl isocyanate, p-bromophenyl isocyanate,
Examples include p-chlorophenylisocyanate, p-)lylisocyanate, p-nitrophenylisocyanate, naphthylisocyanate, and the like.

Furthermore, examples of compounds having an active 10-gen atom include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-
Nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3
-nitro-4-aminobenzenesulfonyl chloride,
2-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride,
Included are 2-amino-5-methylbenzenesulfonyl chloride, phthalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, furoyl chloride, and the like.

In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, colloidal albumin, agar, gum arabic, dextran, alginic acid, such as acetyl content, may be used as a hydrophilic colloid to prepare a silver halide photographic emulsion. Cellulose derivatives such as cellulose acetate hydrolyzed to 19-26%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl cyanoacetate copolymers. , polyvinyl alcohol-polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated flea white matter with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. These hydrophilic colloids can also be used in constituent layers of light-sensitive materials other than emulsion layers, such as intermediate layers, protective layers, filter layers,
It is also used when creating a backing layer, etc.

The silver halide photographic material to which the present invention can be applied may be of any type, such as a black-and-white photographic material, a color photographic material, or a false color photographic material; In addition to photographic materials that can be used for a variety of purposes, such as mechanically negative-type, positive-type,
Examples include all types of photographic materials such as diffusion transfer type materials.

The silver halide emulsions used in these silver halide photographic light-sensitive materials contain all types of halogens such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Silver oxide can be used as a photosensitive component, and this emulsion can contain ruthenium, rhodium, palladium, iridium, platinum,
Noble metal sensitization with salts of noble metals such as gold, such as ammonium chloroparadate, potassium chloroparadite, potassium chloroparadite, potassium chloroaurate, etc., sulfur sensitization with sulfur compounds, reduction with stannous salts, polyamines, etc. Various chemical sensitizations such as sensitization or further sensitization with a polyalkylene oxide compound can be performed.

This emulsion can also be optically sensitized with cyanine dyes, merocyanine dyes, complex cyanine dyes, etc., and various couplers such as colorless couplers, colored couplers, and development inhibitor-releasing couplers, as well as mercury compounds, Stabilizers such as triazole compounds, azaindene compounds, benzthiazolium compounds, zinc compounds, hardeners such as mucohalogen acids, vinyl sulfone compounds, and combinations of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid; Film property improvers consisting of water-dispersible fine particulate polymeric substances obtained by emulsion polymerization of copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc., such as saponin and polyethylene glycol. Coating aids such as lauryl ether and sulfosuccinic acid ester salts, and various other photographic additives may also be added.

The support for the silver halide photographic material of the present invention includes:
Any material such as a film made of polyethylene terephthalate, polycarbonate, polystyrene, polypropylene, cellulose acetate, baryta paper, polyethylene laminated paper, etc. can be used.

Next, the present invention will be illustrated by examples, but the embodiments of the present invention are not limited thereto.

Example 1 After chemically ripening a high-sensitivity silver iodobromide emulsion containing 2.0 mol% of silver iodide, 4-hydroxy-6-methyl 1.333a,
7-chitrazaindene was added as a stabilizer at a concentration of 2.09 per mole of silver halide, and saponin as a coating aid and formalin as a hardening agent were added.

This emulsion contains 61 gelatin per mole of silver halide.
Contains.

The emulsion thus obtained was divided into 19 parts and the coating solution (4 parts) was divided into 19 parts.
).

On the other hand, after preparing a 3% gelatin aqueous solution to which formalin is added as a hardening agent and saponin as a coating aid, it is divided and used as an antistatic agent according to the above general formula (1) or [formerly Compounds represented by, and general formula (
III) polymer (indicated by the number of the above-mentioned exemplified compound).

Or add each of the comparative polymers below to form a coating solution (B).
And so.

Comparative polymer (A): Next, the coating solution (4) was used as the first layer, and the coating solution (B) was used as the second layer, and the coating solution was simultaneously coated on the film so that the second layer was on top of the first layer. and dried to prepare a sample.

The antistatic properties of these samples were investigated using the following method.

b) Observation of the occurrence of static marks The sample was conditioned at a relative humidity of 20% for 24 hours, rubbed with rubber in a dark room under the same air-conditioning conditions, and then subjected to normal development processing. were observed and evaluated based on five levels: "no outbreak,""smalloutbreak,""currentoutbreak,""largeoutbreak," and "extreme outbreak."

口) Measurement of surface resistivity value After conditioning the sample piece under the conditions of 23°C and 20% RH for 24 hours, use an ultra-low current meter manufactured by Kawaguchi Electric (MMA-■-12 model).
One portion was measured using parallel brass electrodes, and the equilibrium value of the indicated value was determined.

The smaller the surface resistivity value, the more electrical conductivity is imparted to the sample, indicating that the antistatic property is better.

As shown in Table 1 above, by using a small amount of the polymer of the general formula (1), the amount of the compound represented by the general formula E(I) or [formula] can be reduced and antistatic properties can be achieved.

Example 2 A highly sensitive silver iodobromide emulsion for X-rays containing 1.5 moles of silver iodide was chemically ripened with gold sensitization and a sulfur sensitizer, and then 4-hydroxy-6 methyl was added as a stabilizer. 1, 3, 3a
, 7-titrazanindine were added in an amount of 2.0 g per mole of silver halide, and predetermined amounts of saponin as a coating aid and formalin as a hardening agent were added, respectively.

This emulsion contains 7 gelatin (B) per mole of silver halide.
Contains i'.

The silver halide emulsion thus obtained was divided into 15 parts to prepare a coating solution for the photosensitive layer.

On the other hand, as in Example 1, the coating solution for the protective layer was prepared in Table 2.
Prepared according to.

These were coated on a polyethylene terephthalate film in the usual manner in the combinations shown in Table 2, solidified, and then dried for 10 minutes under the same drying conditions as in Example 1 to prepare samples.

The thus obtained sample was evaluated for the occurrence of static marks in exactly the same manner as in Example 1.

In addition, with the remainder of the sample, in order to examine the precipitation in the developer, 4 io sheets were processed (processing time 30 seconds, temperature 35°C) per 14 developer solutions for ordinary automatic processors, and then the developer solution was was observed and the degree of precipitation was evaluated in four stages: "no precipitation,""precipitation in progress,""precipitation in progress," and "heavy precipitation."

The results are also shown in Table 2. On the other hand, the photographic properties of these films were also tested using fresh samples of the above configuration.

That is, these films were rated KS-1 based on the JIS method.
After applying wedge exposure with white light using a type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.), it is developed using a continuous roller conveyance type automatic developing machine that can perform development and fixing with a developer using the following development process, washing with water, and drying all at once. Processed.

Developer treatment (Development time: 35°C, 30 seconds) Hydroquinone 10g Anhydrous sodium sulfite
70g Anhydrous sodium borate carbonate (monohydrate) 1-phenyl-1,3-pyrazolidone g 0g 0.3El Sodium hydroxide 5-methylbenzotriazole Potassium bromide glutaraldehyde Bisulfite Add glacial acetic acid water to make 11 .

g 0.05g g 5g g Sensitivity is 1
Shown as 00.

As shown in Table 2 above, by adding the polymer of the general formula (■) in combination, the amount of the compound of the general formula (CD) or (ID) added can be reduced, achieving an antistatic effect and a reduction in precipitation at the same time without impairing photographic properties. can.

Example 3 A silver halide emulsion was prepared in the same manner as in Example 2, divided into nine parts, a polymer of the general formula □□□ or a comparative polymer was added to each as shown in Table 3, and a photosensitive layer was prepared. A coating solution was prepared.

On the other hand, a coating solution for the protective layer was prepared in the same manner as in Example 1, and the combinations shown in Table 2 were coated on a polyethylene terephthalate film in a conventional manner, and after drying, samples were prepared.

Using the sample thus obtained, the surface resistivity value was measured in exactly the same manner as in Example 1, and the following experiment was conducted to observe the image quality of the sample developer.

The sample is exposed to light to give a density value of 1.0 to 1.5, and this is processed using a 90-second processing roller conveyance type automatic developing machine 5AKURA QX, which uses 5AKURA XD90 as a developer and 5AKURA XF as a fixer. -1
200, and the image quality after processing was visually judged.

Depending on the degree of image quality deterioration, the order of severity (in other words, good image quality) is 1) good, 2) somewhat good, and 3.
) Slightly poor, 4) Poor.

The results are shown in Table 3.

As is clear from Table 3, the photosensitive materials of the present invention exhibited good image quality while exhibiting low surface resistivity values.

Claims (1)

[Scope of Claims] 1. A hydrophilic colloid layer of a silver halide photographic light-sensitive material contains at least one of the following general compounds or compounds indicated by [buttons].
1. A silver halide photographic material comprising a species and at least one polymer having an average molecular weight of 106 or less represented by the general formula (1). General formula (I) R-L+CH2CH2O+mH General formula [W [wherein R is a substituted or unsubstituted alkyl group,
Alkenyl group or aryl group, L is 〇1 group, -81 group, N R/ group (however, R' is a hydrogen atom, a substituted or unsubstituted alkyl group, or ÷CH2CH2O+rT
Indicates an IH group. same as below. ), C-N-R' group, or -〇-〇- group,
R1, 111 0 0 and R2 are hydrogen atom, halogen atom, carboxyl group, acyl group, alkoxycarbonyl group, substituted or unsubstituted alkyl group, alkoxy group or phenyl group, R3 is hydrogen atom, methyl group, or α-furyl group represents m
and n represents an integer of 2 to 50. ] General formula [Decoy + A kake B now b [In the formula, A is vinyl alcohol, acrylic acid, meccrylic acid, maleic acid, itaconic acid, carboxystyrene,
Vinyl sulfonic acid, sulfostyrene and alkali metal salts thereof, vinylpyrrolidone, vinyloxazolidinone and the following side chains (M represents an alkali metal atom)
represents a monomer selected from vinyl compounds having B represents a monomer other than A that is copolymerizable with A. a represents 30 to 100 mol%, and b represents 70 to 0 mol%. ]