JPS58196544A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To provide an antistatic photosensitive material generating little static electricity in contact with various substances by incorporating a specified org. compound. CONSTITUTION:A compound represented by general formula I or II is incorporated into at least one of the constituent layers of a photosensitive material. It is preferably incorporated into a layer other than the silver halide emulsion layers, e.g. the surface protective layer, the back layer, the intermediate layer or the undercoat layer. In the formulae I , II, Rf is a 3-20C satd. or unsatd. hydrocarbon group having one or more F atoms substituted for all or part of the H atoms, each of A and B is a bivalent combining group, R1 is H or optionally substituted 1-12C alkyl, each of R2, R3 and R4 is optionally substituted 1-12C alkyl, X is an anion, and each of l1 and l2 is 1, 2 or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material (hereinafter referred to as "photographic material"), and particularly to a photographic material with improved antistatic properties and coatability.

Photographic light-sensitive materials generally consist of an electrically insulating support and a photographic layer. Electric charge often accumulates. This accumulated electrostatic charge causes many problems, but the most serious problem is that the photosensitive emulsion layer is exposed to light due to the discharge of the accumulated electrostatic charge before the processing wall, and the photographic film is processed. In some cases, dot-like spots or dendritic or feather-like line areas are formed, which are called static marks, which can significantly reduce the commercial value of photographic film or, in some cases, completely destroy it. Rule. For example, it will be easily recognized that if it appears in a medical or industrial X-ray film, it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. In addition, these accumulated electrostatic charges may cause dust to adhere to the film surface, or may cause secondary failures such as uneven coating.

As mentioned above, such electrostatic charges are often accumulated during the manufacture and use of photographic materials. For example, in the manufacturing process, it occurs due to contact friction between the photographic film and a roller, or peeling between the support surface and the emulsion surface during the winding and unwinding process of the photographic film. Or, damage caused by contact peeling between X-ray film and a mechanical part or fluorescent intensifying screen in an automatic camera, color negative film, color reversal film, etc. Intimidation machines in photo labs, automatic processing machines that process rubber, metal,
This occurs due to contact peeling of plastic etc. with rollers and pars. It can also occur due to contact with other packaging materials. Static marring of photographic light-sensitive materials induced by such accumulation of electrostatic charges becomes more noticeable as the sensitivity of the photographic light-sensitive materials increases and the processing speed increases. Particularly in recent years, the occurrence of static marks has become even more likely due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photographing, and high-speed automatic processing.

In order to eliminate these problems caused by static electricity, it is preferable that K be added to the photographic light-sensitive material as an antistatic agent. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. That is, in addition to having excellent antistatic properties, antistatic agents that can be used in photographic light-sensitive materials must not have an adverse effect on photographic properties such as sensitivity, fog, graininess, and sharpness of the photographic light-sensitive materials. , the film strength of the photographic light-sensitive material should not be adversely affected (i.e., the film should not be easily damaged by friction or scratching), and the adhesion resistance should not be adversely affected (i.e., the surface of the photographic light-sensitive material should not be easily damaged by surface comrades or other substances). The charging of the photographic material requires performance such as not causing the surface of the photographic material to become easily scratched), not accelerating the fatigue of the processing solution for the photographic material, and not reducing the adhesive strength between the constituent layers of the photographic material. Applying inhibitors is subject to numerous constraints.

One way to eliminate the problems caused by static electricity is to increase the electrical conductivity of the surface of the photosensitive material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged.

Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, certain surfactants, and polymer compounds. I've been exposed to it.

For example, U.S. Pat. No. 2,112,117, 72
, No. 633, 3,0 otsuko, 7? J No. 3, λ42,
No. 107, 3. ! /≠l Utah No. 1, same J, t/r,!
No. 3/, No. 3.713.7/A, No. 3. 31. Polymers such as those described in Tatata et al., for example, U.S. Pat. rijλ.

6yo No. 1, same j, 1 to 21.4cj'4M, 4J, 1
No. 417.074, 3. ≠Yo-, No. 62j, same 3゜!
! λ, No. 272, same j, 43-! , 317, etc., such as those described in U.S. Pat.
No. 042,700, Id.j, 21Aj, No. 133, Id.3. Metal oxides, colloidal silica, etc., such as those described in J2, No. 621, are known.

However, many of these substances exhibit specificity depending on the type of film support and photographic composition, and while they may give good results for certain film supports, photographic emulsions, and other photographic components, others Different film supports and photographic components can be completely useless in preventing static electricity and may also have an adverse effect on photographic properties.

On the other hand, although it has an extremely excellent antistatic effect, it is often unusable because it adversely affects photographic properties such as sensitivity, fog, graininess, and sharpness of photographic emulsions. For example, polyethylene oxide compounds are generally known to have an antistatic effect, but they often have adverse effects on photographic properties such as increased fog, desensitization, and deterioration of graininess.

In particular, for photosensitive materials such as medical direct X-ray photosensitive materials in which photographic emulsions are coated on both sides of the support, it is difficult to establish a technology that effectively imparts antistatic properties without adversely affecting photographic properties. It was difficult. As described above, it is very difficult to apply antistatic agents to photographic materials, and the scope of their use is often limited.

Another method for eliminating problems caused by static electricity in photographic light-sensitive materials is to adjust the electrification series on the surface of the light-sensitive material to reduce the generation of static electricity in response to the above-mentioned rubbing or contact.

For example, British Patent No. 1.330.3jle, ibid.
Yuhiro, No. 631, U.S. Patent Nos. 3 and 6.

No. 1471, 3. jr? , No. 206, Special Publication Showa I2-Yu Otsu No. 7, Japanese Patent Publication No. 1A ≠≦733, same! /-3
No. 2322, No. 13-r'A7/2, No. 2322, No. 13-r'A7/2, Same! ≠−1≠2
Attempts have been made to utilize fluorine-containing surfactants such as those shown in , No. 114, etc., in photographic materials for this purpose.

However, the electrostatic properties of photographic light-sensitive materials containing these fluorine-containing surfactants are generally negatively chargeable, and when combined with a positively chargeable coating agent, etc., a rubber roller with an arbitrary charge series can be formed. Although it is possible to match the charging series of individual materials such as , Delrin roller, and nylon par,
However, with conventional fluorine-containing surfactants, it is difficult to adjust the charge series for all materials. For example, when aligned with the charge series of rubber, dendritic static is created by Delrin, etc. located on the more positive charge series; conversely, when aligned with Delrin, rubber etc. located on the more negative charge series. This causes stain-like static 2,8. Ka, it's always hot. 2. Complementing this, 1. British patent No. 1
．． Uri 3. /! There are methods to lower the surface resistance by using polymer electrolytes as described in No. It has been impossible to incorporate these to the extent that sufficient antistatic properties are obtained.

Next, U.S. Patent No.
．． 110, l, 4c2, JP-A-44-R-yo, λ, 22
No. 3, same! r2-/27.2744. However, it has become clear that these techniques pose difficulties in coating properties during the production of photographic materials.

That is, it is well known that photographic materials are coated with an F coating layer, a silver halide photographic emulsion layer, a protective layer, a filter layer, an antihalation layer, an intermediate layer, etc. on a support such as cellulose acetate, polyester, or polyethylene laminated paper. It is about. When manufacturing photographic light-sensitive materials consisting of many layers, these coating liquids are coated with "hajiki" (i.e.,
It is required to uniformly apply a thin layer without causing coating failures such as small areas repelling the coating liquid and leaving it uncoated. Further, in producing photographic light-sensitive materials, a support is often coated with multiple layers of photographic emulsions and other gelatin-containing coating solutions at the same time. For example, this is the case when three or more separate photographic emulsion layers are successively coated to produce a color photographic material. When applying gelatin or other colloid liquid to such a gelatin colloid layer, it is more difficult to obtain the required coating properties than when applying gelatin colloid liquid directly to the support. This is especially true when the underlying coated layer is a wet, cool-set layer immediately after coating. The fluorine-containing cationic surfactants described above have been studied as antistatic agents, but most of them have poor coating suitability, especially in high-speed coating, and are susceptible to problems caused by insoluble matter called "comecite", dust, etc. This may cause localized incomplete application, ``repellency,'' or uneven application. Therefore, in order to solve these problems, US Patent No. 31,771,124, oi3. Otsu No. 26 discloses a technology that uses a nonionic surfactant in combination.

However, these are useful only with specific photographic coating solutions or specific coating conditions, and lack versatility. Furthermore, the use of nonionic surfactants also causes the problem of desensitization in terms of photographic performance. The first objective of the present invention is to provide an antistatic photographic material that exhibits less static appearance when used with solid materials. When applying photographic coating solutions containing various photographic binders or without binders in a thin film at high speed, it is possible to obtain a uniform suspension and avoid defects such as "repellent" and "gomet". An object of the present invention is to provide a photographic light-sensitive material that can obtain a uniform coating film without any scratches.

A third object of the present invention is to apply the first and third gelatin-containing layers to a photographic layer containing gelatin even when the gelatin-containing layers are passed through separate coating machines, or when multilayer coating is carried out simultaneously or sequentially on an undercoat layer. It is an object of the present invention to provide a photographic material which can be easily coated even in the case of a photosensitive material and which has improved coating properties such as nozzle and flaking.

The V object of the present invention is to provide a photograph containing a fluorine-containing cationic surfactant that does not have an adverse effect on photographic performance. This was achieved using a silver halide photographic material characterized by the following.

General formula CL) 2 However, f is a saturated or unsaturated hydrocarbon group in which all or part of the hydrogen atoms have been replaced with fluorine atoms11).1 The number of carbon atoms is 3 to -Zl17. , B represents a divalent linking group.

几 is a hydrogen group, a substituted or unsubstituted alkyl group with carbon number i and tλ, R2, RU3, 几. represents a substituted or unsubstituted alkyl group having 1 to 1 carbon atoms; X represents an anion; 0 and β2 are integers of 7 to 3;

Examples of the divalent group represented by A in the general formulas [I] and [■] include the following.

Q) Lf O2 O- 1 Examples of the covalent group represented by B in Table 6 include the following.

+CH21D(-CH2+-2゜ l Here, D is 10-1-S-1-COO-.

However, p, m, m2, ni, and n2 represent integers of og. Examples of X in general formulas [I] and [■] include the following F.

(y3, Br, I, NOa
, CHaCO (J.

In the H3SO3 general formula, 几0, 几2, 几3, PL4, R5, a
Examples of the heptavalent rt substituent include a hydroxy group, an alkokino group, an arylox/group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an epoxy group, a carbamoyl group, and the like. Particularly preferred substituents include a hydroxy group, an alkoxy group, an epoxy group, and an alkyloxycarbonyl group.Next, typical examples of compounds used in the present invention are listed.

Compound Example 0H2C1-120H CHCONH2H Next, a specific example of the method for synthesizing the compound 1 used in the KIIZ of the present invention will be shown.

Synthesis Example 1 (Compound sequence/U component 3-aminopyridine?, ≠/f chloroform<ros
t) Add 70 octanoyl chloride to the solution
After refluxing 3,3f/ under a nitrogen stream for 7 hours and cooling, 30θwl of diethyl acetate was added, and the mixture was washed with 2N caustic soda water and water, and ethyl acetate was distilled off. The remaining solid content was recrystallized from an acetonitrile (1-chloroform (2tOd) bath), washed with acetonitrile, and dried under vacuum. Yield: 32g.

The above-obtained j-(N-per70-octanoyl)aminopyridine 217-0j and methyl p-toluenesulfonate, 3f, were heated under reflux in 10sl of methanol for 3 hours.

After cooling, 200 td of ethyl acetate was added to collect the precipitated crystals, which were further recrystallized from 200 td of acetone. Yield/Ri, Hiro y rarely.

Synthesis Example 2 (Synthesis of Compound 7) N-Methylbi is Radin toy, Triethylamine j
In a solution of Og in 2 r Oml of chloroform,
1 Fluorooctanoyl fluoride-ZJ'A
After cooling at room temperature and heating under reflux for 3 hours, reaction 11i was washed with caustic soda and water, the chloroform layer was concentrated under reduced pressure, and the residue was crystallized with ethyl acetate. . After filtration, wash with ethyl acetate and place in a desiccator.
Dry under medium pressure. Yield 10. Free, melting point is t6~6
The above amine 10. lAf is ethylene bromohydrin 22. After reacting with J''9 at 70°C for 3 hours, acetonitrile jOs/ was added and the precipitated crystals were again recrystallized with acetonitrile!Od.

Yield 7.0f/, /10~200 decomposed at 0C.

The compound of the present invention is added to at least one of the constituent layers of the photographic light-sensitive material, and such constituent layers include layers other than the silver halide emulsion layer, such as a surface protective layer, a back layer,
Preferably, it is an intermediate layer, an undercoat layer, or the like. When the back layer consists of two layers, either layer may be used, or it may be used as an overcoat on the surface protective layer.

In order to exhibit the effects of the present invention most prominently, it is preferable to add the compound of the present invention to a layer, a surface protective layer, a backing layer, or an overcoat layer.

In order to apply the compound used in the present invention to a photographic light-sensitive material, the compound is dissolved in water or an organic solvent such as methanol, isopropanol, acetone, etc., or a mixed solvent such as 7N, etc., and then a surface protective layer or back layer is formed. It can be added to coating solutions such as dip coating, air knife coating, or U.S. patent
, by the extrusion coating method using Hola/Tai- as described in Kota No. 3, or by the method described in U.S. Patent No. 3. ro
t.

2nd layer No. 7, same Ko, Rihiro/, tPr No. 3. j24.1
21, etc., layers of λ or more are applied simultaneously, or immersed in an antistatic liquid.

Further, if necessary, an antistatic liquid containing the compound of the present invention is further coated on the protective layer.

The amount of the compound of the present invention to be used is preferably o, oooi-co, op, and particularly preferably 0.0001 to 0.0j da per square meter of the photographic light-sensitive material.

However, the above range may of course vary depending on the type of photographic film base used, the photograph, the composition, the form or the coating method.

Supports for the photographic material of the present invention include, for example, cellulose nitrate film, cellulose acetate film, cellulose acetate; y'-y-
There are laminates of these films, etc., and more specifically, baryta or α-olefin polymers, especially polyethylene, polypropylene. , 2-1 carbon atoms such as ethylene-butene copolymer
Paper coated or laminated with a polymer of 0 α-olefins may be mentioned.

In the photographic light-sensitive material of the present invention, each photographic constituent layer may also contain the following binder.

For example, hydrophilic colloids include proteins such as gelatin, colloidal albumin, and casein; cellulose compounds such as carboxyl/methyl cellulose, and hydroxyethyl cellulose; agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and polyvinyl alcohol; Examples include -N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, derivatives 2 and partial hydrolysates thereof, and the like. Mixtures of two or more of these colloids are used if necessary.

Among these, gelatin is the most used, and gelatin here refers to so-called lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin.

In addition to being able to replace part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, i.e., amino groups, imino groups,
It is also possible to replace the hydroxy group or carboxyl group with one treated or modified with a reagent having one group capable of reacting with them, or with a graft polymer in which molecular chains of a polymeric substance are bonded.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually a water-soluble silver salt (for example, nitric acid filtrate) solution and a water-soluble halide salt (for example, potassium bromide) solution.
! 1 in the presence of a water-soluble polymer solution such as gelatin. This silver halide includes silver chloride,
In addition to silver bromide, mixed silver halide such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used.

Photographic emulsions can be subjected to spectral sensitization or superchromatic sensitization as necessary by using polymethine sensitizing dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. .

Furthermore, various compounds can be added to the photographic emulsion of the photographic light-sensitive material used in the present invention to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material. These compounds are ≠-hydroxy-2-methyl-/,! -, 3a.

7-tetrazaindene-3-methyl-benzothia:/-
Silver halide photographic emulsions are color photographic light-sensitive materials that have been known for a long time, including many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts, including phenyl-mercaptotetrazole. When used as a silver halide emulsion layer, the coupler may be included in the silver halide emulsion layer. Examples of such couplers include ordinary type diketomethylene yellow couplers, 2-equivalent type diketomethylene yellow couplers, high-equivalent or λ-equivalent type pyrazolone magenta couplers, indashilon magenta couplers, α-naphthol type Noan couplers, and phenol. A cyan coupler or the like can be used.

The silver halide emulsion layer and other layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardeners (singly or in combination). Typical examples include mucochloric acid, formaldehyde, trimesololmelamine, glyoxal, 2,3-dihydrox7-/,
≠-Aldehyde compounds such as dioxane, λ, 3-dihyde, roxy-methyl-/, hi-dioxane, succinic aldehyde, and glutaraldehyde; divinyl sulfone, methinon bismaleimide, i, 3. r-Triacryloyl-hexahydro-3-triazine, /, j,
j-) Rivinylsulfonyl-hexahydro-8-to IJ
7 Dinbis(vinylsulfonylmethyl)ether, 1
13-bis(vinylsulfonylmethyl)furopanol-
2. Active vinyl compounds such as bis(α-vinylsulfonylacetamido)ethane; λ, ≠-dichloro-t-hydroxy7-3-triazine sodium salt, λ, IL-
Active halogen compounds such as dichloro A-methoxy-3-) riazine;2. ≠, 6-doriethylene imino S-
Examples include ethyleneimine compounds such as triazine.

A surfactant may be added alone or in combination to the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, sensitization and other photographic property improvements, and charge sequence adjustment.

These surfactants include natural surfactants such as naponin, alkylene oxide type, glycerin type, clinodol type etc., surfactants, higher acyl amines,
High class ammonium salts, pyridine and other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums; anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester, phosphoric acid ester, amino acids, aminosulfonic acids, sulfuric acid or phosphorus of amino alcohols; It is divided into amphoteric surfactants such as acid esters.

Some examples of surfactant compounds that can be used include U.S. Pat.
same! , 21rr, 221. No. 2.73? ,
19/issue, same j, 01. ! , 10/issue, same 3゜/rr
, ≠ r+ issue, same 3. Yu0/, No. 213, 3.2io
, iyi issue, 3.22≠,! ≠θ No. 3. IAI
! , t'Ari issue, same J, IA≠/, ≠13, same J, 4
4≠λ, 6 and φ, same 3. ll-73-, No. 17≠, 3. ! 44, No. 7744, 3. Otsu 6 Otsu.

≠No. 7, No. 3,307.41zO, British Patent No. 1,
Ryohei Oda et al. [Synthesis of surfactants and their applications (Maki Shoten, /ri 6tA) and A, W
, "Surface Active 1 Agents" by Perry (Interscience/<Flication Incorporated,/5'j!Nii;-), J.

P, / Three "Enocyclo is Tier of Active Agents Volume λ" (Chemical Bubbles 7.:L
In the present invention, formulas (1), (if), (I
7 elemental surfactants other than the compound represented by I) can be used in combination, and examples of such fluorine-based surfactants include the following compounds. ,j! No. 6, same/, J-2≠
, No. 3/, U.S. Patent No. 3°414, No. 7r, No. 3.
rlY, YO6, Tokko Akira-MLA Otsu? No. 7, Tokukai Sho Ik? There are fluorine-based surfactants described in RI-6733, RI-3232-L, and the like.

In addition, in the present invention, lubricating compositions such as U.S. Pat. No. 3,077.137, U.S. Pat. ! ≠! , No. 270, No. 3, U.S. Pat.

The photographic light-sensitive material of the present invention is disclosed in US Pat.
．． ≠/1. No. 77, 3. ≠//, Ri No. 71, Machikoaki≠! -1331, etc., and may also contain silica, He strontium, barium sulfate, polymethyl methacrylate, etc. as matting agents.

In the photographic constituent layers of the photographic light-sensitive material of the present invention, US Pat.
．． 1!3, 5F2/issue, same! , 707, 37th issue, 3rd, 27th/, /3rd issue, 3rd, 7th issue ≠.

≠ Ri No. 3, same 1.49! Ultraviolet absorbers such as those described in No. 1, No. 07, No. 1, Dohiro, No. 1, No. 1, Tatata, and JP-A No. 3/14620 can be incorporated by emulsion dispersion or latex dispersion.

According to the present invention, failures caused by static during the manufacturing process and/or use of photographic materials have been improved.

For example, in the practice of the present invention, contact between the emulsion side and the back side of a photographic light-sensitive material, contact between the emulsion side and the emulsion side 2, and materials with which photographic light-sensitive materials commonly come into contact, such as rubber, gold, plastic, etc. The occurrence of static marks caused by contact with fluorescent screens and the like was significantly reduced.

Next, the effects of the present invention will be specifically explained with reference to Examples, but the invention is not limited thereto.

Example 1 Approx./7! Samples /-/ to /-j, each consisting of an emulsion layer and a protective layer stacked on one side of a μ polyethylene terephthalate film support in this order, were coated and dried according to a conventional method. The composition of each layer is as follows.

(Emulsion layer: approx. jμ) Binder: Gelatin =, 1! m2 coating silver;z! /m2 Halogenation *= formation; AgI/, jmo1%2 and AgB
r3'J', jmo1% fog suppressant;/-phenyl-! -Mercaptoterrasil o, to ryl g/00 f (protective layer; approx. lμ) Binder; Serratia/, 79,7m2 Coating agent: N-oleoyl-N-methyltaurine sodium salt 7q/m2 NJIE agent; -2,≠- Jikkoro Otsu-Hydroxy/
, 3. j'-) riazine lysium salt O0≠y/100
9 Gelatin Here, sample l/ consists only of the above composition, sample/-2
In addition to the above-mentioned composition, the protective layer contains compound examples /, 2, and // of the present invention, respectively.

j da/m2 included.

In addition, for comparison, in addition to the above composition, samples lj containing the comparative compound /,jlq//m2 in the protective layer were prepared. Comparative Compound A: 1 To evaluate the coating properties of these samples. Next, the number of ``Hajichi'' present per 7 square meters of the sample was observed with the inner eye.

Two more unexposed samples! 'C, 2! %) After conditioning the humidity with LH for 2 hours, the sample was rubbed with a rubber roller and a Delrin roller in the same air-conditioned dark room, developed with the following developer, fixed, and washed with water to create a static image. Checked the mark occurrence #.

(Developer composition) Hot water troo resistant sodium tetrapolyphosphate λ, Oy anhydrous sodium sulfite soy Hydro Chitsuno 1
0g Sumisaka sodium (/water salt) ≠ay/-7
22-3-pyrazolidone 0.39 potassium bromine
2. Add water
lOθO resistance (pH 10, 2) The results of the antistatic properties and coating properties of these samples are shown in the first column.

In the table above, the evaluation of the degree of static mark occurrence is A; the occurrence of static marks is clearly not observed; B;
〃 Slightly recognized C; tt
tt is recognized as D; 〃
〃 It was divided into 44 stages based on whether it was recognized almost completely.

As is clear from Table 1, the samples prepared using the anti-static coating of the present invention have an excellent antistatic effect with almost no static marks observed, and have excellent coating properties. It can be seen that there is no adverse effect on the On the other hand, in the control, the banding prevention was significantly inferior, and in the sample /-j used for comparison, although the band'1 prevention was slightly improved, the applicability deteriorated.

Implementation row 2 Three vinegar iron 7 lulose support, Halley 7 Yo/Prevention-1 red sensitivity source layer, A/5 layer, rim 1 deceptive layer, yellow filter 7#, Yoi 1
Meiko #2: Groove formation 7'1. Samples λ-/, 2-2, λ-3 and λ-4t were coated and dried according to the method. The composition of each layer is shown below.
ing.

(Anti-halation layer) Binder; Gelatin≠,≠f/m'' Hard 1 (agent; /, J-His(vinylsulfonyl)-propanol Roule /, 2 (//100f bar 1゛/der) Coating aid: Dodecylbenzenesulfone sodium acid 41cai
qim2 antihalation component; black colloidal silver O0≠da/m2 (red photosensitive layer) binder; gelatin 797m2 N pesticide; /, j-bis(vinylsulfonyl)-propanol-2 /, 2y7iooy binder coating aid;
Sodium dodecylbenzenesulfonate/Oq/m
2 Coated silver amount; 3, / l / m ``Halogen specific composition HAgI 2 mol % and Ag lBr mol mol y'' Reduction inhibitor; ≠-Hydroxy-B-methyl-/,
j, Ja, 7-chitrazaindene. , riy/A g
/ 009 Q coloring agent; /-Hydroquine-≠-(niacetylphenyl)azo-N-(g-(,z,!-G-tert-amylphenoxy/butyl)~λ-su7doamide 3♂no/Ag
/θ09 Sensitizing dye; anhydroj,j/-dichloro-2-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyaninohydroxide 7dopyridinium salt 0,j
(//J” 4 layers g / 00 f (middle N) Pa (7 d: Seeyfy2, I!lf/m2 hardener;
/, 3-bis(vinylsulfonyl)-pronozenol-J /, 21//θ0g, seasonal coating aid; sodium dodecylbenzenesulfonate/λr, 4/
,,t2 (green photosensitive layer) Binder; Gelatin 2. ≠fI/m 2d film agent:
/, j-his(vinylsulfonyl)-pucobanol-2/, 21/100! Binder coating aid; Sodium dobuflubenzenesulfonate If/m"t4hi yt, 7Mo #% Stabilizer; Hiro-Hydrox 7-A-Methyl-7,3゜3a,
7-Titrazainoden□, 4f/Ag00f1 Color former;/-(-Z,≠, O-trichlorophenyl)-
3-(3-(Z,≠-di~tert-amylphenoac)acetamide 1benzamide-≠-(4IL~methoxy7phenyl)ahe-tavirazolone 3fy/8g100
f Sensitizing dye; acihydro-! , j'-diphenyl-2-ethyl-3,3'-di(neesulfoethyl)oxycarbonoamine hydroxytopyridinium salt o,3y/Ag
1ooy (yellow filter Iig) binder; gelatin 23 y/m 2 filter component; yellow colloid urine□, 7f/m2Njlll;/,
j-bis(vinylsulfonyl)-polymer/-ru, l
/ , 2f/100Lj by 7der world j active left cut; Yu ~
17 ml/m2 (1, °6 original layer) Binder; Gelatin 797 m2 Hard agent; /, J-His(vinylsulfonyl)-
Propanol-a/,,tt/10of/binder coating aid; sodium dodesolbenzenesulfonate IJ cum fq/m2 coating 4mi; -2, -2y/m2 halogenated X
1 composition; 13.3 mol of Ag and 6.7 mol of λgBry; ≠-hydroxy7-6-methyl/, 3°3a
, 7-Chitrazai/De10. ≠y/Az0OQ light color r1];λ'-chloro-! ′-[nee(2,≠-n-tert-'7'milfenoki/)butyramide]-
α-(j,j'-dimethyl-2,'A-dioxo3-
oxazolidinyl)-α-(≠-methoxybenzoyl)
Acetanilide≠r f /Ag/lyo y (protective layer) l (I/D; gelati/2 y/m 211g agent;
/, 3-His(vinylsulfonyl)-probanol rouille /, 2f/100f Binder one Fabric aid: Sodium dioctyl sulfosuccinate T/m2 Mantifying agent: Copolymer of polymethyl methacrylate and polymethacrylate 7- (Copolymerization ratio B: ≠ average particle size λ
, jμl100'llf/W12 sample 2-/ consists only of the above composition, and samples 2-u, u-3, 2'-≠ have the above composition as well as the uninvented compound 1 example 3 in its protection i-, and Comparative Compound -Ai in g q/m 2 each. These samples were examined for antistatic properties and coatability ft in exactly the same manner as in Example 1, except that ordinary color development was carried out.
1 The results are shown in Table 41.

As is clear from Table 2, the samples using the compounds of the present invention were found to have significantly improved antistatic properties without deteriorating coating properties.

On the other hand, when these samples were exposed according to the JIS method and subjected to normal color development processing, in Sample 2 using the comparative compound, severe desensitization occurred in the blue, green, and red light-sensitive layers. With the compounds of the present invention, almost no adverse effects on photographic properties were observed.

Example 3 A back layer and a protective layer for the back layer were provided on one side of a cellulose triacetate support, and an antihalation layer, a red photosensitive layer, an intermediate layer, a green photosensitive layer, a yellow filter layer, a blue photosensitive layer and a blue photosensitive layer were provided on the opposite side of the cellulose triacetate support. Samples and materials (J
-/), (j-2), (j-j), (j-4) and (
3-j was applied and dried according to a conventional method. The composition of each layer is shown below.

(Back layer) Binder; Lime-treated gelatin B, 2y/m2 salt; Potassium nitrate, iy/y12 iH agent; l,3-bis(vinylsulfonyl)-propanol-2 0.49/100 nopy/da Protective layer) Binder; Lime-treated gelatine, 2 f 7' m
2 Matting agent; Polymethyl methacrylate (1,800 particle size 2, jp) 20111/m 2f film agent;
/ , 3-bis(vinylsulfonyl)-iaA/-
#-J/, 21/1009 binder 10owg/m
2 Harenyon prevention layer The following components were the same as in Example λ, and the protective layer was the same as Sample-1 λ.

Sample (J-/) consists only of the above composition, and sample (j-2
), in addition to the composition of sample (J-/), compound 3 of the present invention was added to the protective layer of pack 1- in 7. ! da/m2, sample, fee (j-
Similarly, jl is 3q/m2 of the compound example of the present invention≠, sample (
3-Hiroshi), each compound r was added my/m2. Further, as a comparative sample, Compound B was added to the composition of sample (J-/), and the protective layer of the pack layer contained it at 3 wg/m2 to prepare sample (J-2).

The antistatic properties and coating properties of these samples were investigated in the same manner as in Example 1, except that the back surface was rubbed against a rubber Delrin roller, and the results are shown below.

As is clear from Table 3, the samples using the compounds of the present invention were found to have significantly improved antistatic properties without deteriorating coating properties.

Example 4 In the same manner as in Example 2, a cellulose triacetate support, an anti-ration layer, a red light-sensitive layer, an intermediate layer, a green light-sensitive layer, a yellow filter layer, a blue light-sensitive layer, and a lower protective layer having the composition shown below. and the sample values configured by stacking the upper layer of the protective layer in this order -no~≠-t
was applied at rjm/min according to a conventional method and dried.

(Protective layer lower layer) Binder: Gelatin 1.4/m2 Hard 11HI/lj-bis(vinylsulfonyl)-probanol/, At/1009 Binder coating aid: Dioctylsulfocono-sodium phosphate! II
I/m2 Ultraviolet absorber; (protective layer upper layer) Binder; Osseic acid-treated gelatin (isoelectric point 7) If
/mW hardener; /, J-bis(vinylsulfonyl)-zolopanoreuille i, xy/1ooy binder matting agent;
Copolymer of polymethyl methacrylate and polymethacrylate (copolymerization ratio j:j average particle size 3μ) jt17
Cape/m2 Polymethyl methacrylate (average particle size 3μ) 10 da 7
m2 Sample≠-7 consists only of the above composition, and samples≠-2・≠-3
, ≠-Hiroshi, ≠-j is in addition to the above composition, Compound Example 7 of the present invention
and Comparative Compound C. The coating properties and antistatic properties of these samples were investigated in the same manner as in Example λ, and the results are shown in Table ≠.

As is clear from Table 1, the antistatic properties of the samples using the compounds of the present invention are greatly improved without deteriorating the coating properties. On the other hand, the comparative compound cannot simultaneously satisfy antistatic properties for Delrin and rubber rollers even if the amount is changed. In addition, samples using the compound of the present invention (Hiro-
(Y) to (Hiro-9L) have good wetting and spreading of the developer, and there is little development unevenness and bubbles adhering to the film surface, but (lA-1), especially (≠-B), where comparative compounds were used, The developer is not wet properly.

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by containing a compound represented by the following general formula [I] or (II). General formula [I] However, f is a saturated or unsaturated hydrocarbon group in which all or a part of the hydrogen atoms are replaced with fluorine atoms, and the number of carbon atoms is 3 to 0. AXB represents a divalent linking group.几represents a hydrogen group or a substituted or unsubstituted alkyl group having 1 to IO carbon atoms, and B2, R3, and B4 represent a substituted or unsubstituted argyl group having 1 to IO carbon atoms. X represents an anion, A1, A! 2 is an integer from 1 to 3.