JPH02184842A - Silver halide photographic sensitive material having improved antistatic property and coatability - Google Patents

Abstract

PURPOSE:To obtain an antistatic silver halide photographic sensitive material enabling high-speed coating without causing trouble such as foaming or repelling by forming at least one hydrophilic colloidal layer on a support and incorporating a specified compd. into the layer. CONSTITUTION:At least one hydrophilic colloidal layer is formed on a support and at least one kind of compd. represented by formula I is incorporated into the layer. In the formula I, R<1> is alkyl, alkenyl, alkylaryl or aralkylaryl, R<2> is H or methyl, A is 2-4C optionally substd. alkylene, Y is H or SO3M, M is H, an alkali metal atom, ammonium or alkanolamine, m is an integer of 1-200 and n is an integer of 1-100. The antistatic property and coatability of the resulting silver halide photographic sensitive material can be improved without adversely affecting the photographic characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to antistatic silver halide photographic light-sensitive materials, and more specifically, the present invention relates to antistatic silver halide photographic light-sensitive materials, and more specifically, a halogenated silver halide photographic material that has improved antistatic properties and coatability without adversely affecting photographic properties. Related to silver photographic materials.

[Background of the invention]

In recent years, demands for silver halide photographic materials (hereinafter referred to as photographic materials or simply "photosensitive materials") have become increasingly complex and diverse. There is also a demand for photosensitive materials with high image quality.

In particular, for X-ray photosensitive materials, in order to reduce the amount of X-rays the human body is exposed to, high sensitivity and high image quality are used to obtain more information with a smaller amount of X-rays, and rapid development is required to obtain information quickly. A photosensitive material that is suitable for processing is desired.

Since photosensitive materials generally consist of an electrically insulating support and photographic constituent layers, electrical charges are lost during the manufacturing process of the photosensitive material and during use due to contact friction or peeling between the surfaces of the same or different materials. is likely to accumulate. The photosensitive emulsion layer is sensitized by the discharge of electrostatic charges accumulated before processing, resulting in dot-like spots or dendritic or feather-like line spots, so-called static marks, when photographic film is processed. . This significantly reduces the commercial value of photographic film. For example, static marks that appear on medical or industrial X-ray films can lead to very dangerous judgments, but this phenomenon becomes apparent only after the film is developed, and is one of the most troublesome problems. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface or inability to apply uniformly. These static marks are becoming more likely to occur due to the increased sensitivity of photosensitive materials, high speed coating, high speed photography, high speed automatic processing, etc.

Methods have been considered to improve the conductivity of photosensitive material supports and various coated surface layers, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. .

However, many of these substances may exhibit specificity depending on the type of support or photographic composition, or may have an adverse effect on photographic performance. In particular, it is extremely difficult to prevent static electricity on a hydrophilic colloid layer, and the surface resistance may not be sufficiently reduced at low temperatures, and adhesion failures often occur between photosensitive materials or other substances at high temperatures and high humidity. .

Furthermore, although they have an antistatic effect, such as polyethylene oxide compounds, there are many that have adverse effects on photographic properties, such as increased fog, desensitization, and deterioration of graininess.
- It has been difficult to find antistatic agents suitable for use in light-sensitive materials such as Ray-sensitive materials, which have emulsion layers on both sides of the support.

In connection with the above-mentioned generation of static electricity due to contact friction or peeling, it is also important to improve the sliding properties of the surface of the photosensitive material.

In other words, various roller equipment used in manufacturing processes such as coating, drying, processing and packaging of photosensitive materials, as well as film loading, photographing, processing in automatic processors, and photocopying.
Alternatively, there are extremely many opportunities for contact friction between sensitive materials.

Therefore, improvements in the sliding properties of photosensitive materials are required, in addition to antistatic properties, to prevent scratches and scratches on the surface caused by friction, and to improve film transportability, as well as to reduce the sliding friction of photosensitive materials. Ru.

Representative studies that have been proposed in the past include US Patent No. 3, which uses organosiloxanes.
, No. 042,522, JP-A-60-140342, and JP-A-62-2649.

Although each of these known improvement means improves the slipperiness to some extent, it is not always satisfactory, as it is not sufficient or deteriorates other properties such as peeling chargeability.

On the other hand, during production of photographic light-sensitive materials formed from hydrophilic colloid layers, it is required that these coating solutions be coated in a thin layer uniformly and at high speed without causing repelling or uneven coating. In producing light-sensitive materials, coating solutions containing photographic emulsions and other hydrophilic colloids such as gelatin are often simultaneously coated on a support in multiple layers. Obtaining the required coating properties when applying gelatin or other organic colloid liquids to such organic colloid layers, such as gelatin, is more difficult than when applying gelatin colloid liquids directly to the support. Accompany. This is especially true when the underlying layer is in a cool set state immediately after coating.

Various surfactants (hereinafter referred to as activators) have been used as coating aids and emulsifiers in various coating solutions for photosensitive materials, or as additives for improving the surface properties of photographic surface layers.

In particular, saponin has been widely used as a coating aid in the photographic industry, but it has drawbacks such as easy foaming, large fluctuations in quality because it is a natural product, and poor properties as a coating aid. In addition, various other synthetic activators have specific effects on the coating properties and surface characteristics of various photographic coating solutions or photographic coating layers depending on the type of activator, and therefore their range of use is limited. Different types of active agents are selected and utilized depending on the particular application.

However, some of these have unsatisfactory photographic properties, especially deterioration of film properties at high temperatures and high humidity, insufficient stability of the compound itself, or insufficient high-speed coating properties.

[Purpose of the invention]

Therefore, the present invention has been made in view of the above circumstances, and a first object of the present invention is to provide an antistatic silver halide photographic material that can be coated at high speed without bubbles, smudges, or other coating failures. Our purpose is to provide photosensitive materials.

A second object of the present invention is to provide a silver halide photographic material with improved surface slipperiness.

A third object of the present invention is to provide a silver halide photographic material that is antistatic using an antistatic agent that does not adversely affect photographic performance.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support and containing a compound represented by the following general formula CI) in the hydrophilic colloid layer. achieved.

2 General formula CI) In the formula, R1 is an alkyl group, alkenyl group, alkylaryl group, or aralkylaryl group having 8 to 30 carbon atoms, and examples of the alkyl group include octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl. , tetradecyl, pentadecyl, hexadecyl, heptadecyl,
Examples include octadecyl, nonadecyl, eicosyl, and the like.

Examples of the alkenyl group include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,
Heptadecenyl, octadecenyl, etc.

As the alkylaryl group, monobutylphenol,
dibutylphenol, 5ec-butylphenol, di5
Examples include ee-butylphenol, tert-butylphenol, octylphenol, nonylphenol, dinonylphenol and the like.

Examples of the aralkylphenol include styrylphenol, benzylphenol, cumylphenol, etc., and a mixture of these alkyl groups may be used. R2
is a hydrogen atom or a methyl group.

Further, A is an alkylene group or substituted alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene, butylene, imbutylene, etc., and may be a single group or a block or random mixture thereof.

Y represents a hydrogen atom or a -303M group. M is a hydrogen atom, an alkali metal atom, an ammonium metal atom,
Displays alkanolamine groups.

n is an integer from 0 to 100, m is an integer from l to 200,
More preferably, n is 0 or 1-50, and m is 2-100.

Next, specific examples of the compound represented by the general formula CI) of the present invention will be shown, but the present invention is limited thereto. The above surfactant according to the present invention can be easily synthesized, such as A surfactant can be obtained by using nonylphenol or lauryl alcohol as a raw material, heating and reacting glycidyl methacrylate in the presence of a catalyst, and adding alkylene oxide to the resulting reaction composition.

Details of these are described in JP-A-63-185436.

The compound of general formula (1) according to the present invention can be used in hydrophilic colloid layers (silver halide emulsion layers, intermediate layers,
It may be added to any layer (filter layer, antihalation layer, protective layer, etc.), but it is preferably added to the protective layer and/or emulsion layer.

The amount added is not constant depending on the type of photosensitive material, layer structure, etc., but it is preferably used in the range of JOB to 10g per coating liquid IQ, particularly preferably 100mg to 5g.

In addition, in the case of a silver halide emulsion, it is added during chemical ripening, after chemical ripening, and/or just before coating the emulsion, but it is more preferable to add it at the end of chemical ripening of a silver halide emulsion. be.

When the compound of the present invention is used in combination with an anionic activator,
Antistatic performance is improved. The anionic active agent used in combination is not particularly limited. The amount of anionic activator used is
Preferably 1Qmg-10g per 1ρ of coating liquid 100m
g to 5 g is particularly preferred.

When the compound of the present invention is used in combination with a polyoxene ethylene activator in addition to the anionic activator, more favorable effects can be obtained. In this case, the compound of the present invention, anionic activator, and polyoxyethylene activator may be added to the same coating solution or to separate coating solutions.

It is not preferable to use cationic additives or anionic additives in the same solution, as the reaction may cause various failures (coating failure, desensitization, fogging, etc.).5. However, it is particularly preferred that the compounds of the invention be used in systems containing cationic additives and anionic activators. Although the mechanism is not clear, coating failure, desensitization, increased fog, etc. can be significantly reduced by adding the compound of the present invention.

As cationic additives, in addition to the sensitizing dyes and activators shown below, Japanese Patent Publication Nos. 48-34166 and 50-4066
For example, the fog suppressant described in No. 5 may be mentioned.

(Sensitizing dye) RN(CH3)3Xe R: Furkyl As the silver halide emulsion used in the light-sensitive material of the invention, any commonly used silver halide can be used. Further, the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, and may be polydisperse or monodisperse.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may have a regular crystal shape such as a tetrahedron or a dodecahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape.
Alternatively, it may have a composite form of these crystal forms.

It may also consist of a mixture of particles of various crystalline forms.

Also, for example, a junction type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, a silver halide crystal grown epitaxially, (for example, silver chloride on silver bromide, Silver iodobromide, silver iodide, etc. are grown epitaxially.

) A hexagonal crystal, a crystal in which a regular hexahedral silver chloride is aligned over a regular octahedral silver iodide, or the like may be used.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area. For details, see Japanese Patent Publication No. 58-1279.
It is described in specifications such as No. 21 and No. 58-113927.

It is also possible to use a combination of internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2086.

In carrying out the present invention, the silver halide grains used in the silver halide emulsion may be prepared by the neutral method, acidic method, ammonia method, forward mixing method, back mixing method, double jet method, etc., which are well known in the photographic field. Chondrold double jet method,
It can be manufactured by applying a method such as a congersion method or a core/fel method.

Another form of the double jet method is the triple jet method in which soluble halogen salts of different compositions are added independently (for example, soluble silver salt, soluble bromine salt, and soluble iodide salt).
can also be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced, ie, a so-called Chondrald double jet method, can also be used.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In addition, these silver halide grains or silver halide emulsions contain iridium, thallium, palladium, rhodium,
It is preferable that at least one salt (soluble salt) of zinc, nickel, cobalt, uranium, thorium, strontium, tungsten, and platinum is contained. Its content is preferably between 10-' and 10-' per mol Ag.
'It's a mole. Particularly preferably, at least one of thallium, palladium, and iridium salts is contained. These may be used alone or in combination, and the addition position (time) is arbitrary. This is expected to improve flash exposure characteristics, prevent pressure desensitization, prevent latent image regression, increase sensitization, and other effects.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include Research Disclosure's RD-17643 and RD additives shown in the table below, chemical sensitizers, sensitizing dye development accelerators, antifoggants, stabilizers, color stain inhibitors, and image stabilizers. Ultraviolet breathing agent Filter Dye enhancer Self-curing agent Coating aid Surfactant Plasticizer Slip agent Static inhibitor Matting agent Binder RD-17643 Page Classification 23 llI 23 rV 29 llI 24 VI l/ ■ ■ 25 〜26 ■ 26〜27 26〜27 ■ VI RD-18716 Page Classification 648- Upper right 648 Right-Upper right 648- Upper right 649- Lower right〃 65〇-Left-Right 649 Right~650 Left 651 Right 650 Right 650 Right〃 650 Right 650 Right 26 II 651 Right Examples of supports that can be used in the photosensitive material of the present invention include those described in the left column of page 28 of the aforementioned RD-17643 and page 647 of RD-18716. It will be done. Suitable supports include polymer films, paper, etc., which may be treated to enhance adhesiveness, antistatic properties, etc.

The photosensitive material according to the present invention is the above-mentioned RD-17643-2.
Development processing can be carried out by the usual method described on pages 8 to 29 and on page 651 of RD-18716, left column to right column.

This photographic processing method may be black and white photographic processing for obtaining recorded images or color photographic processing for obtaining color images. The processing temperature applied to photographic processing is usually 18°C ~
Although the temperature is 50°C, the treatment can be performed at a temperature lower than 18°C or higher than 50°C.

Photographic materials to which the photographic emulsion of the present invention can be applied include:
Mention may be made of various color and black and white photosensitive materials.

For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, or may or may not contain couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, color photosensitive materials for heat development, plate making Photographic materials (lithographic film, scanner film, etc.), X-ray photographic materials (direct/indirect medical use, industrial use), black and white negative film for photography, black and white photographic paper, microphotosensitive materials (00M)
color diffusion transfer photosensitive materials (D
TR), silver salt diffusion transfer photosensitive materials, printout photosensitive materials, and the like.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 2 mol% of iodine and 0.2 mol% of chlorine with an average particle size of 0°3 μm
A silver iodobromide layer with a ratio of 40 mol% of iodine and 60 mol% of bromine is provided on the inner core of monodispersed silver chloroiodobromide containing iodine and on the outside thereof, and is grown to a grain size of 0.5 μm. A silver iodobromide layer was grown to a size of 0.85 μm at a ratio of 1 mol % and bromine 99 mol % to obtain slightly rounded dodecahedral silver halide grains.

These particles were chemically ripened by adding chloroaurate, rhodanammonium, sodium thiosulfate, and thiourea compounds.

4-hydroxy-6- as a stabilizer per 70 g of these particles.
An emulsion preparation solution was prepared by adding 2 g of methyl-1,3,3a,7-chitrazaindene. Various additives and coating aids shown in Table 1 were added to this emulsion adjustment solution and the protective layer solution shown below.

Next, the emulsion liquid was coated on a polyethylene terephthalate support with a silver content of 4.8 g/m2 and a gelatin content of 3.8 g/m2.
5g/m2. The protective layer liquid has a gelatin content of 1.0g/
Simultaneously apply at 150 m/min so that the
Twenty-six types of samples were prepared by drying for 0 seconds.

Emulsion additive (per mole of silver halide) t-butylcatechol 400mg Polyvinylpyrrolidone (molecular weight 10,000) 1. Og styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane 10 g Diethylene glycol nitrophenyl triphenylphosphonium chloride 1,3-dihydroxybenzene-4 Ammonium sulfonate 2-mercaptobenzimidazole-5- Sodium sulfonate 5.0 g 0mg g 5mg CH2C00(CH2)9CH3 CHCOOCHzCHzCI((CHs)to3Na rng C, HsOC82C1(CH2N(CH2COOH)2
H 1,1-dimethylol-1-bromo-1-nitromethaneg Off1g Protective layer additive (per 1g of gelatin) NaOsS CHC00CHz (CJa) JCH2C
00CF+, (C,F4),)1mg CsF+eOyunCH2CH,0CI(fficH20
H3°gC, FSSO, K
2 mg Matting agent made of polymethyl methacrylate with an average particle size of 7 μm
7mg average grain 10.013μ heel colloidal silica
70mg formaldehyde 3
1I1g glyoxal 21
! 1g2-hydroxy-4,6-dichloro-1,3,5
- Triazine sodium salt 3 mg The antistatic performance, photographic performance and coating performance of the sample thus obtained were examined by the following methods.

l) Measurement of the amount of static marks The unexposed sample was conditioned for 2 hours at 23°CCl2O%RH, then rubbed with a rubber roller in an air-conditioned dark room, and then processed using an automatic processor 5RX-501 (manufactured by Konica Corporation). ) was processed for 45 seconds using a developer for an X-ray automatic processor, XD-SR, and a fixer, XFSR (both manufactured by Konica Corporation), and the antistatic performance of the added compound was investigated.

The degree of occurrence of static marks is evaluated visually. The evaluation criteria are as follows.

A: It does not occur at all.

B: Occurs over 3% of the area.

C: 3% or more by area D = Occurs in an area of 10% or more.

2) Measurement of surface specific resistance To measure the surface specific resistance value, the sample piece was conditioned for 24 hours at 23°C and 20% RH, and then used with an ultra-microcurrent needle (Model MMA-VI-12 manufactured by Kawaguchi Electric Co., Ltd.). ) and brass parallel electrodes, measurements were taken for 1 minute and the equilibrium values of the indicated values were determined.

The smaller the surface resistivity value is, the better the antistatic property is because the sample is imparted with conductivity.

3) Measurement of photographic performance The prepared sample was exposed to white light using a tungsten lamp using a KS-1 sensitometer manufactured by Konica Corporation in accordance with the JIS method, and then developed in the same manner using the above-mentioned automatic developing machine. The photographic performance was measured. The sensitivity is expressed as a relative value when the sensitivity of sample 1 is set as 100, and the fog +
Calculated from the exposure amount that gives a density of 0.20.

4) Measurement of coating performance (2) Coating unevenness was evaluated by the following test method.

A sample with a width of 30 cm and a length of 100 cm is uniformly exposed to light so that the density becomes 1.0, and the developed sample is visually judged.

Evaluation of coating unevenness> ◎: Very good O: Good △: Slightly poor ×: Poor ■The number of comments per 1I112 was investigated for each sample.

Note that the comments refer to "Film Coating Theory J" by Deryagin et al. (B, M, Deryagins S, M, Levi
, FilmCoating Theory, The
Focal Press, 1964) P, 183, minute amounts of oil particles, mineral oil particles, hydrophobic liquids, and solids contained in the coating liquid serve as a core, and the coating is applied locally including the surrounding area. refers to a phenomenon that causes parts that are not

In addition, for samples 1-17.22 to 26, each antistatic agent was added to the protective layer, and for samples 19 to 21,
It was added to the emulsion layer, and for sample 18,
The exemplified compounds are added separately to the protective layer and the emulsion layer.

comparative compound ■) Saponin CH.

C8H17NΦ-CH3Bre CH.

■) Surfactant ACaF+ySO2NCH2CH20SO3Na(n
= 120-170) These results are also shown in Table-1.

As is clear from Table 1, the samples that were antistatic using the present invention had fewer static marks, had better coating properties, and had the same photographic performance as the comparative samples. It turns out that there are no negative effects. Although the amount added was varied in Samples 11 to 13, it can be seen that an amount around 3 Q mg/'m2 is most preferable in terms of photographic performance, antistatic performance, and coating properties.

Furthermore, the effect is particularly noticeable in samples in which the exemplified compound is used in combination with a fluorine-containing surfactant or a polyoxyethylene-based surfactant.

Example 2 The following layers were sequentially coated on a transparent support made of subbed cellulose triacetate film and having an antihalation layer (containing 0.38 g of black colloidal silver and 3.2 g of gelatin). Color photosensitive material sample 27-42 was prepared. In the following examples, the amount added to the light-sensitive material is shown per 1 m2, and the amount of silver halide emulsion and colloidal silver is shown in terms of silver.

Layer 1: 1.3 g of low-sensitivity red-sensitive silver iodobromide (containing 5 mol % silver iodide) emulsion sensitized to red, 1.3 g of gelatin and 0.7 g of 1-hydroxy-N[ δ−
(2,4-di-t-amylphenoxy)butyl 12-naphthamide (cyan coupler), 0.07 g 1-hydroxy-4-[4-(1-hydroxy-δ-acetamide-3,6-disulfo-2 -naphthylazo)phenoxy]-N-[δ-(2,4-di-t-amylphenoxy)butyl-2-naphthamide disodium (colored cyan coupler) and 0.07 g of 4-octadecylsuccinimide-2-(i A low-speed red-sensitive emulsion layer containing 0.7 g of tricresyl phosphate (TCP) in which phenyl-5-tetrazolylthio)-1-indanone (DIR compound) is dissolved.

Layer 2: 1.2 g of highly sensitive red-sensitive silver iodobromide emulsion (6 mol%
of silver iodobromide), 1.4 g of gelatin and 0.2
0,2 in which 0g of the cyan coupler used in layer 1 and 0.02g of the colored cyan coupler used in layer 1 were dissolved.
Highly sensitive red-sensitive emulsion layer containing 2g of TCP.

Layer 3: Intermediate layer containing 0.05 g dibutyl phthalate (DBP) and 0.7 g gelatin dissolved in 0.05 g 2.5-di-L-octylhydroquinone (antifouling agent).

Layer 4; Color sensitized to green sensitivity? 1.90 g of low-sensitivity green-sensitive silver iodobromide (containing 5 mol% silver iodide) emulsion and 2.1 g
of gelatin and 0.8 g of 1-(2,4,6-drichlorophenyl)-3-([α-(2,4-di-7-amylphenoxy)-acetamido]benzamide)-5
- Pyrazolone (magenta coupler), 0.15 g 1
-(2,4,6-1-lichlorophenyl)-4-(1 naphthylazo)-3-(2-chloro-5-octadecenylsuccinimide anilino)-5-pyrazolone (colored magenta coupler), 0. DI used in layer 1 of 016g
A low-speed green-sensitive emulsion layer containing 0.95 g of TCP in which the R compound was dissolved.

Layer 5: 1.7 g of high-sensitivity green-sensitive silver iodobromide emulsion (containing 4 mol% silver iodide) color sensitized to green, 1.9 g of gelatin and 0.20 g of magenta used in layer 4. A high speed green sensitive emulsion layer containing 0.60 g of DNP dissolved in the coupler and 0.049 g of the colored magenta coupler used in layer 4.

Layer 6: 0,1 dissolved in 0.15g yellow colloidal silver, 0.2g antifouling agent (same as contained in layer 3)
Yellow filter layer containing 1 g DBP and 1.5 g gelatin.

Layer 7: 0.25 g of low-speed blue-sensitive silver iodobromide emulsion (containing 4 mol% silver iodide) color-sensitized to blue sensitivity and 1.9 g
of gelatin and 1.5 g of α-pivaloyl = (1-
Benzyl-2-7enyl-3,5-dioxoimidazolidin-4-yl)-27-chloro-5'-[(σ-dodecyloxycarbonyl)ethoxylponylcoacetanilide (yellow coupler) was dissolved. A low-speed blue-sensitive emulsion layer containing 0.6 g of TCP.

Layer 8: 0.9 g of highly sensitive blue-sensitive silver iodobromide emulsion (containing 2 mole % silver iodide), color sensitized to blue, 1.5 g of gelatin and 1.30 g used in layer 7 A high-speed blue-sensitive emulsion layer containing 0.65 g of TCP in which a yellow coupler was dissolved.

Layer 9: Protective layer containing 2.3 g of gelatin, O.1 g of an exemplary compound of the invention or a comparative compound. A hardening agent and a spreading agent were added to each layer.

The sample prepared as above was heated at 23°C, 123%RH.
After rubbing the sample with a rubber roller and a nylon roller in a dark room under the same air-conditioning conditions for 12 hours, the following development process was performed to evaluate the degree of static marks as shown in Example 1.
Judgment was made in the same manner.

Regarding the slipperiness of the film surface, the coefficient of friction was determined using the method described below, and regarding the coating performance, unevenness and number of comets were determined using the same method as in Example 1.

Evaluation by static friction coefficient t, anvelt, j, r, carol,
jr, and 1. j.

sugdenj, smpte, 80 [9] ]7
The maximum static friction coefficient of the film surface after coating was determined using the paper clip method described in 34-739 [1971].

A smaller value means less friction on the film surface.

[Development treatment prescription 1 Processing time Color development
3 minutes 15 seconds (38°C)
White 6 minutes 30 seconds water
Wash 3 minutes 15
Second fixation 6
Wash with water for 30 seconds
Stabilization bath for 3 minutes and 15 seconds The composition of the treatment liquid used in each treatment step was as follows.

[Color developer] Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N
-β-Hydroxyethylamino)-2-methylaniline sulfate 4.5g water is added to give IQ.

[Bleach solution] Ammonium bromide 160.0g Ammonia water (28%) 25.0m
Q Ethylenediaminetetraacetic acid sodium iron salt 130.0g Add glacial acetic acid water to obtain IQ.

[Fixer] Sodium tetrapolyphosphate sodium sulfite Ammonium thiosulfate (70%) sodium bisulfite Add water to obtain IQ.

[Stabilizing liquid 1 Formalin (37% aqueous solution) Add water to obtain IQ.

14.0m+2 2.0g 4.0g 175.0mQ 4.6g 8.0m (2) As is clear from the results in Table 2 above, the implementation of the present invention improves antistatic performance even in the case of color multilayer films. , improvements in coating properties and friction properties have been obtained.

〔Effect of the invention〕

According to the present invention, it was possible to obtain a silver halide photographic material having excellent antistatic performance and coatability without adversely affecting photographic properties.

Moreover, such an effect became even more remarkable when a polyoxyethylene-based or fluorine-based surfactant was used in combination, and it was also excellent in reducing the coefficient of friction on the film surface.

hand Continued Supplementary Positive book Heisei December 18, 1 year

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one hydrophilic colloid layer on a support, which layer contains at least one compound selected from the following general formula [I]. A silver halide photographic material characterized by: General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents an alkyl group, an alkenyl group, an alkylaryl group, or an aralkylaryl group. R^2 represents a hydrogen atom or a methyl group, and A represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms. Y is a hydrogen atom or SO
_3M group, where M represents a hydrogen atom, an alkali metal atom, an ammonium group, or an alkanolamine group. m represents an integer of 1 to 200, and n represents an integer of 1 to 100. ]