JPH01101545A - Silver halide photographic sensitive material which is improved in antistatic performance and coatability - Google Patents

Abstract

PURPOSE:To obtain good coatability and antistatic performance by incorporating specific compds. into a photosensitive material. CONSTITUTION:The compd. expressed by the formula I and/or at least one kind of the compds. expressed by the formulas II-V are incorporated into at least one layer of a photosensitive material. In the formulas I-V, R1 denotes higher alcohol having an alkyl group, alkenyl group of 8-22 C or alkyl phenol ethylene oxide having an alkyl group of 4-12 and/or residual group added with propylene oxide; R2 is OH or OR1. R3, R5 are alkyl groups or alkenyl groups of respectively 8-22 and 7-21 C; A is ethylene or propylene; R4 is a hydrogen or (AO)nH; n is 1-50 integer; R5 is COR5 or (AO)nH; X is 0-3 integer; R7 is (AO)nH, A-N(R4)2, etc. The good coating performance and the excellent antistatic performance are thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material that is antistatic, and more particularly to a silver halide photographic material that is antistatic without adversely affecting photographic properties. .

[Background of the invention]

In recent years, the demands on silver halide photographic materials (hereinafter referred to as photographic materials or simply referred to as light-sensitive materials) have become increasingly complex and diverse.In particular, the demands for silver halide photographic materials (hereinafter referred to as photographic materials or simply "photosensitive materials") have become increasingly complex and diverse. Materials are requested.

In particular, in the case of XH adverse photosensitive materials,
In order to reduce the amount of radiation exposure, a photosensitive material is desired that has high sensitivity and high image quality so that a large amount of information can be obtained with a smaller amount of XIIA, and that is suitable for rapid development processing in order to obtain information quickly.

Photosensitive materials are generally exposed to electrically insulating supports and photographic constituent layers, so they are subject to electrostatic charge during the manufacturing process and during use due to contact friction or peeling between the surfaces of the same or different materials. Charges tend to accumulate, and the photosensitive emulsion layer becomes sensitized by discharging the accumulated electrostatic charges before the development process, and when the photographic film is developed, dot-like spots or dendritic or feather-like lines, etc. This results in so-called static marks. This seriously reduces the commercial value of photographic film. For example, static marks that appear on medical or industrial X-ray film can lead to extremely dangerous judgments, but this phenomenon only becomes apparent after it is developed. This is one of the most troublesome fortune-telling. 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 higher sensitivity of photosensitive materials, commercial 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 exhibit specificity depending on the type of support and the composition of the photosensitive material, and while they may give good results for certain supports, photographic emulsions, and other photographic components, they may Supports and photographic components are left with gaps that are completely useless in preventing static electricity, and may even adversely affect photographic performance. Furthermore, even if the antistatic effect is excellent, it is often impossible to use it because it adversely affects photographic properties such as sensitivity, fog, graininess, and sharpness of the photographic emulsion.

In addition, the antistatic agent must not have any negative effect on the film strength of the photographic light-sensitive material, must not have a negative effect on the adhesion resistance, should not accelerate the fatigue of the processing solution for the photographic light-sensitive material, and must not have any adverse effect on the film strength of the photographic light-sensitive material. Performance such as not reducing the adhesive strength between the constituent layers is required.

On the other hand, in the production of photographic materials formed from many woody organic colloid layers, it is extremely important to apply these coating liquids to a uniform thickness over the entire surface.

However, in reality, there are often cases of vertical unevenness, horizontal unevenness or cissing, localized coating called comets, serious failures, and even kinks and chips where the coating liquid gathers around the coated surface and becomes thicker, or conversely recedes and becomes thinner. This tends to cause uneven coating. For this reason, natural or synthetic surfactants have traditionally been used as coating aids for various coating solutions.
Only a limited number of surfactants are put to practical use because they only give good results with certain photographic coating solutions, have insufficient coating performance, or have a negative effect on photographic properties. be. Furthermore, the number of surfactants that can be effectively used in multilayer coatings is further reduced to a very small number.

In recent years, with the demand for mass production of photosensitive materials, it is not uncommon for photosensitive materials to be coated at faster coating speeds than conventional ones, for example at speeds of 100 m/min or more.In such high-speed coating, coating failures occur more than ever before. Furthermore, there is an increasing demand for thinner films to improve photographic performance and processability, and further improvement in coating properties is desired in high-speed thin film coating.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a product with good coating properties without adversely affecting photographic properties, and with good antistatic performance under various storage and usage conditions. The purpose of the present invention is to provide a photographic material that can display the following characteristics.

[Structure of the invention]

As a result of various studies, the present inventors have discovered that a specific phosphoric acid ester type surfactant and/or nitrogen-containing surfactant can achieve the initial objective, and have accomplished the present invention. That is - the above object of the invention provides that at least one
In a photographic light-sensitive material having a hydrophilic colloid layer and a photosensitive silver halide emulsion layer, at least one layer contains f.
Achieved by a photographic material containing at least one of the compounds represented by the general formula (1) and/or the compounds represented by the general formulas (2), (3), (4), and (5). Ta.

General formula (1) (However, R is an alkyl group having 8 to 22 carbon atoms, a higher alcohol having an alkenyl group, or an alkylphenol having an alkyl group having 4 to 12 carbon atoms, and 1 to 1 to 1 mol of ethylene oxide or/and propylene oxide. 10
0 mole added residue, R2 is OH or OR, nH, n is an integer from 1 to 50.

) General formula (3) General formula (4) (However, R3 is an alkyl group or alkenyl group having 7 to 21 carbon atoms, R6 is CORs or (AO)nH, and x is an integer of 0 to 3.) General Formula (5) % Formula % A (NA) y R*, where y is an integer of 1 to 3, and R is a more specific description of the present invention.

First, the phosphate ester type surfactants represented by the general formula (1) are octyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, cetyl alcohol, oleyl alcohol, and surfactants with 11 carbon atoms according to the Oxon method. ~! 1 to 100 mol of ethylene oxide or/and propylene oxide by a known method to 1 mol of higher alcohol such as a mixed alcohol of 5 or a secondary alcohol having 12 to 13 carbon atoms.
Nonionic surfactant with molar addition; Nonionic surfactant with 1 to 100 moles of ethylene oxide or/and propylene oxide added to 1 mole of alkylphenol such as butylphenol, octylphenol, nonylphenol, dodecylphenol, dinonylphenol, etc. as raw materials. 0.3 phosphorus oxychloride, phosphorus pentoxide, preferably phosphorus pentoxide, is added to 1 mol of these raw materials by a known method.
It is obtained by reacting ~1 mol.

Preferred in terms of performance are lauryl alcohol, tridecyl alcohol, oleyl alcohol, a mixed alcohol having 11 to 15 carbon atoms from the Oxon method, octylphenol,
5 to 15 ethylene oxide to 1 mole of nonylphenol
It is preferable to use a nonionic surfactant with molar addition as a raw material.

Nitrogen-containing surfactants represented by general formulas (2) to (5) (hereinafter referred to as aminoether type surfactants) include octylamine, decylamine, dodecylamine, myristylamine, palmitylamine, cetylamine, Stearylamine, tallow amine, behenylamine, lauryl aminopropylamine, tallow aminopropylamine, higher fatty acids such as lauric acid, myristic acid, valmitic acid, stearic acid, oleic acid, ethylenediamine, propylene diamine, aminoethylethanolamine, R5C0NHCHaCH20H, R5C0 (NHCHa
CHz)zOH,RsCO(NHCH2CH2)2MH
z, R5C0(NHCHzCHt)2CH2NH2, R
5C0(NHCH2CH1,)2NICOR,,R5C
0(NHCH, CH2) 38Hz, R1C0(NHC
H2CH2)3NHCOR5, R5C0(NHCHzC
Ht) 48Hz, R, C0 (NHCH2CH2), Nl
It is a nonionic surfactant that uses an amide compound or imidacillin compound such as ICOR, etc. as a raw material and adds 1 to 100 moles of ethylene oxide and/or propylene oxide to 1 mole of these raw materials.

Preferred in terms of performance are dodecylamine, myristylamine, palmitylamine, cetylamine, stearylamine, tallow aminopropylamine, C,yH3scO(NH
CHzCHz)tNH*, C,? H3,C0(NHC
H2CH2)3NHCOC1? A 7-minoter type surfactant in which 5 to 20 moles of ethylene oxide is added to 1 mole of H22, is preferred.

Typical specific examples of compounds represented by general formulas (1) to (5) (hereinafter referred to as compounds of the present invention) used in the present invention are shown below, but the present invention is not limited thereto.

8. Compound Cl 1lH3 represented by general formula (1)? o(CH3COO). . POJ2self5
HasO(CH2CHzOh.PO3H2Cl J2y
O(CH2CH20) +5POJtB General formula (2)
Compound B-I CIJ33NH(CH2Cl,0)JB-
2C,,H3? NH(CH3COO),. HCH3C Compound CI represented by general formula (3) ClxHzsNHCH2CHzCH2NH (
CH2CH2O)<oHC2C+oH*+NHCHzC
HtNH(C)lzcHO)J■CI.

D Compound represented by general formula (4) D-I Cl7H2SCO (NHCH2CH2N
H(CI2C820)l. HD2ClsH3
*C0NH(CI2)sNHcHzcH2NH(CHz
CIIO): +HCH.

D3C+dbsCO(NCHzCHz)
2NHcOc+Jss(CH2CHzO)ml ( E Compounds represented by general formula (5) Regarding the synthesis of these compounds, see JP-A-60-715
You can refer to No. 26.

The compounds of the present invention may be used alone or in combination of two or more, particularly preferably a phosphoric ester compound of general formula (1) and an amino ether of general formulas (2) to (5). The method is to use any of the type compounds together.

When the compound of the present invention is used as an antistatic agent for a photosensitive material, the amount added is not particularly limited.
The range is preferably 0.001 to tog per 112, more preferably 0.01 to 5 g.

When the compound of general formula (1) and the compounds of general formulas (2) to (5) are used together, -m at least one of the compounds of formula (1)
It is preferable to use 20 to 500 parts by weight of at least one of the compounds represented by formulas (2) to (5) based on 100 parts by weight of the seed.

In addition, the compound of the present invention and other surfactants can be directly added to each layer constituting the photosensitive material, such as a protective layer, a silver halide emulsion layer, a filter layer, a subbing layer, a backing layer, etc. They can be added to the same coating solution, or they can be added in the form of a solution by first dissolving them in a suitable solvent, such as water, alcohol, dioxane, glycol ether, or a mixed solvent thereof. May be added.

In addition, in the present invention, the lubricating composition includes, for example,
US Patent No. 3,079,837, US Patent No. 3,080,3
No. 17, No. 3,545.970, JP-A-52-129
Modified silicones such as those shown in No. 520 can be included in the photographic constituent layers.

The light-sensitive material of the present invention has U.S. Pat.
No. 11,911, No. 3,411,912, Special Publication No. 1973
-5331 etc., and as a matting agent, silica, barium sulfate 1. Strontium sulfate, polymethyl methacrylate, etc. can be included.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

The silver halide grains in the silver halide emulsion may have a regular crystal structure such as a cube, an octahedron, or a dodecahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape. having an irregular crystal shape,
Alternatively, it may have a composite form of these crystal forms.

Furthermore, Research Disclosure (RHHr6hDi)
sclosure, hereinafter abbreviated as RD L Volume 225, 2
2534, pp. 20-58 (1983), or internal latent image type silver halide grains and surface latent image type halogenated grains described in Japanese Patent Publication No. 41-2088. A combination with silver particles can also be used.

The photographic emulsion used in the present invention is
(P, GIafkides) Mr. Chisie et
PhysiquePhotography)J*
Published by Paul Nontel (1)
967), C1F, Duf
fin) IF r7 Photographic Emullenotane 0 Chemistry 4 (Photographic E
+*ulsion Cbemistry) J*The Focal Press (1966), V. El Zelikman et al.
Making and Coating P
photographic Ea+ulsion)",
It can be prepared using the method described in The 7 Orcal Press (1964).

The silver halide emulsion may be chemically sensitized by sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. known in the art, or a combination thereof, and may also be spectrally enhanced by methine dyes or the like. good.

As binders for the photographic constituent layer, proteins such as gelatin and casein; cellulose compounds such as carboxymethylcellulose and hydroxyethylcellulose; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, acrylic acid copolymers, or , synthetic hydrophilic colloids such as their hydrolysates, etc. can be used. Gelatin here refers to so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, and modified gelatin.

Examples of the support used in the photosensitive material of the present invention include polyolefins such as polyethylene, polystyrene,
cellulose derivatives, such as cellulose triacetate,
Included are supports made of polyester films such as polyethylene terephthalate, or sheets of baryta paper, synthetic paper, or paper coated on both sides with these polymer films.

The support used in the present invention can also be provided with an antihalation layer. For this purpose, mention may be made of carbon black or of various dyes, such as oxonol, azo, styryl, anthraquinone, merocyanine and tri(or di)arylmethane.

In addition, chemical sensitizers, spectral sensitizers, anti-capri agents, stabilizers, hardeners, plasticizers, lubricants, coating aids, whitening waste, ultraviolet absorbers, and couplers used in the photosensitive material of the present invention. , color image stabilizers, etc., are not particularly limited; for example, RD,
Volume 176, 17643.22-28] (1978
) can be referred to.

The photosensitive material of the present invention includes ordinary black-and-white photosensitive materials (photosensitive materials for photography, X-ray photosensitive materials, photosensitive materials for printing, black-and-white photographic paper, etc.), and ordinary color photosensitive materials (photosensitive materials such as photosensitive materials,
(color photographic paper, color reversal film, etc.), silver salt diffusion transfer process, die trans7ar process, silver dye bleaching method, heat-developable photosensitive materials, etc.
It is particularly effective for high-temperature, rapid processing photosensitive materials and high-sensitivity photosensitive materials.

Regarding the processing of these photosensitive materials, please refer to L, F, ^, Mason Ij [
7t Togera Quick Processing φ Chemistry
(Photographic Processing
CI+ea+1stry) J, The 7 Ocal φ Pre Joining Publication (1975) and RD, Volume 176, 17643 (
The descriptions in 28-31 above can be referred to.

〔Example〕

The present invention will be explained in more detail by showing specific examples below.

Example 1 2 mol% of iodine and 0.2 mol% of chlorine with an average particle size of 0.3 μ-
A silver iodobromide layer was provided on the inner core of monodispersed silver chloroiodobromide containing and on the outside thereof in a ratio of 40 mol% iodine and 60 mol% bromine, and was grown to a grain size of 0.5 μ-. A silver iodobromide layer was grown to a thickness of 0.85 μm at a ratio of 1 mol % iodine and 99 mol % bromine to obtain slightly rounded dodecahedral silver halide grains.

Chlorauric acid salt, rhodanammonium, sodium thiosulfate, and thiourea-based compounds were added to these particles for chemical ripening.

4-hydroxy-6- as a stabilizer per 70 g of these particles.
Methyl-1=3.3a and 2 g of 7-chitrazai methine were added to prepare emulsion 7IR liquid preparation. Various additives and coating aids shown in Table 1 were added to this emulsion adjustment solution and the protective layer solution shown below.

The emulsion was then deposited on a polyethylene terephthalate support with a silver content of 4.8 g/m'' and a gelatin content of 3.8 g/m''.
5g/m2, and the protective layer liquid has a gelatin content of 1.0g/m2.
A sample was prepared by simultaneously applying the coating at a rate of 150+* per minute so as to obtain l12 and drying for 2 minutes and 30 seconds.

Emulsion additives (per mole of silver halide) t-butylcatechol 400mg polyvinylpyrrolidone (molecular weight 10,000) 1.0g styrene-maleic anhydride copolymer 2.5g trimethylolpropane 10g diethylene glycol 5.0g nitrophenyl trichloride Phenylphosphonium chloride 50mg1.3
-Dihydroxybenzene-4- Ammonium sulfonate 4g 2-Mercaptobenzimidazole-5-Sodium sulfonate 15mg 70g C4+1,0CII□CHCH2N (C112COO former 2舊OHIg l, 1-dimethylol-1-promo 1-nitromethine 7c theory g Protective layer additives (per 1 g of gelatin) CH2COO (CH2), CH.

■ CHcoo (C)12) CH2Cl (CI,) 27mg
SO*Na (n is a mixture of 2 to 5) C,F, ,0-(CII2CI20 juice o CH2CH
20H3m gC4FISO3K
Matting agent made of polymethyl methacrylate with an average particle size of 2 mg and 7 μm
-70 g colloidal silica with average particle size of 0,013 μm 70 mg formaldehyde
3B Glyoxal
2B2-hydroxy-4,6-dichloro-1
,3,5-triazine sodium salt
3. The antistatic performance, photographic performance and coating performance of the sample thus obtained were examined in the following manner.

1) Measurement of the amount of static marks The unexposed sample was conditioned at 23°C and 23% RH for 2 hours, and then rubbed with a rubber roller and a nylon roller in a dark room under the same air conditioning conditions. Development $1VX-4
00 (manufactured by Konishiroku Photo Industries Co., Ltd.) for 90 seconds with X-ray automatic processor developer XD-90 and fixer XF (both manufactured by Konishiroku Photo Industries Co., Ltd.) to prevent static electricity of the added compound. I checked the performance.

2) The degree of occurrence of static marks was evaluated visually. The evaluation criteria are as follows.

A: It does not occur at all.

B: Occurs in less than 3% of the area.

C: 1 immersion of 3% or more by area D = Occurs in 10% or more of the area.

3) Measurement of photographic performance The prepared sample was exposed to white light using a tungsten lamp using a KS-1 sensitometer manufactured by Konishiroku Photo Industry Co., Ltd. based on the JIS method. The photographic performance was measured using the developed method. The sensitivity is expressed as a relative value when the sensitivity of sample 1 is set as 100. Calculated from the exposure amount that gives a density of fog +0.20.

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

A sample with a diameter of 30 cm and a length of 100 cm was uniformly exposed to light to give a density of 1.0, and the sample after development was visually evaluated.

<Evaluation of coating unevenness> ° ◎: Very good O: Good Δ: Slightly poor ×: Poor ■ The number of repellents per 112 was examined for each sample.

For samples 1 to 20, 23 to 26, 28 to 30, each surfactant was added to the protective layer, and for sample 21, it was added to the emulsion layer.
For example, the exemplified compound was added to the protective layer and the emulsion layer separately.

comparative compound ■) Saponin ■) CH.

C, H,, -NΦ-CH30re CH.

(n=120 to 1i0) These results are shown in Table 1. In the table, capri is the value obtained by subtracting the base concentration.

I ゛、! As is clear from Table 1, the samples that were antistatic using the compound of the present invention produced fewer static marks and had better coating properties than the comparative samples, and did not have any negative effects on photographic performance. It turns out that there is no effect. Also,
When the exemplified compound is used alone, the added amount is 3011Ig/l112 in terms of photographic performance, antistatic performance, and coating properties.
Nearby is most preferable.

Furthermore, when a phosphate ester type surfactant and a 7-minoteter type surfactant are used in combination, the effect is particularly excellent.

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). Samples 31-4
3 was created. In addition, in the following examples, the amount of additive material added to the photosensitive material is per 112,
In addition, silver halide emulsions and colloidal silver are shown in terms of silver.

Layer 1: 1.3 g of 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-monoamylphenoxy)butyl]-2
-su7 toamide (cyan coupler), 0.07g 1
-Hydroxy-4-[4-(1-hydroxy-δ-7cetamido3,6-disulfo-2-su7tylazo)phenoxy]-N-[δ-(2,4-di[-7milphenoxy)butyl- 0.7 g in which 2-su7tamidotanosodium (colored cyan coupler) and 0.07 g of 4-octadecylsuccinimide-2-(1-7-5-tetrazolylthio)-1-indanone (DIR compound) were dissolved. triphrenor phosphate) (T
A low-speed red-sensitive emulsion layer containing CP).

Layer 2: 1.2 g of highly sensitive red-sensitive silver iodobromide emulsion (6
mol % of silver iodobromide), 1.4 g of gelatin and the cyan coupler used in layer 1 of O, ZOg and 0.0
A high-speed red-sensitive emulsion layer containing 0.228 TCP in which 2 g of the colored cyan coupler used in layer 1 was dissolved.

Layer 3: 0.05. 2,5-7-t-octylhydroquinone (antifouling agent) dissolved in 0.05 g of butyl 7-talate (DBP) and 0.7 g of gelatin.

Layer 4: 0.90 g of low-sensitivity green-sensitive silver iodobromide (containing 5 mol% silver iodide) emulsion color-sensitized to green sensitivity and 2.1 g
of gelatin and 0.8 g of 1-(-2,4,6-trichlorophenyl)-3-([α-(2,4-not-
amylphenoxy)-7cetamido]benz7mido1-
5-pyrazolone (magenta coupler), 0.15 g of 1-(2°4.6-trichlorophenyl)-4-(1-
0.95 g of the DIR compound used in WJl was dissolved in 0.016 g of A low-speed green-sensitive emulsion layer containing TCP.

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 in which the colored magenta coupler used in layer 4 was dissolved.

Layer 6: Yellow filter layer containing 0.15 g yellow colloidal silver, 0.11 g DBP dissolved in 0.2 g antifouling agent (same as contained in layer 3) 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 a-piparoyl-(1-
Benzyl-2-phenyl-3,5-quoxoimigzolidin-4-yl)-2'-chloro-5'-[(α-dodecyloxycarbonyl)ethoxycarbonyl]acedoanilide (yellow coupler) was dissolved. , eg, a low-speed blue-sensitive emulsion layer containing TCP.

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

Layer 9: 2.3. of gelatin, 0.1 g of an exemplary compound of the present invention or a comparative compound: Ji/! !
1. A hardening agent and a spreading agent were added to each layer.

The sample prepared as described above was heated to 23% R1+ at 23°C.
After adjusting the temperature at 12:00 and 11:00 under the same air-conditioning conditions and rubbing with a neoprene rubber roller and a nylon roller with different charge series in a dark room under the same air-conditioning conditions, the following development process was performed to check the degree of static marks using the same method as in Example 1. It was judged.

In addition, the number of repellents per 112 samples was examined for each sample, and coating unevenness was evaluated. The determination of coating unevenness was carried out in the same manner as in Example 1, except that the development process was replaced with the following color development process.

[Development processing prescription] Processing time Color development
Bleach for 3 minutes and 15 seconds (38℃)
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Washing with water for 6 minutes and 30 seconds Stabilizing bath for 3 minutes and 15 seconds The composition of the treatment liquid used in each treatment step was as follows.

[Color developer 1 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
Add 4.5g water to make 11.

1 white liquor 1 ammonium bromide 160.0 g aqueous ammonia (28%) 25. (h1 Ethylenediaminetetraacetic acid sodium iron salt 130.0g Glacial acetic acid 14.On+j!
Add water to make 11.

[Fixer 1 Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0+++1 Sodium melon sulfite 4.6g Add water to make 11.

[Stabilizing liquid] Formalin (37% aqueous solution) 8.0 Add 111 water to 1
Set to 1.

The results are shown in Table-2.

The sample of the present invention did not exhibit any particular increase in Capri concentration or decrease in sensitivity compared to the comparative sample.

Margins below [Effects of the Invention] As described above, the present invention provides an antistatic agent of the general formula (
By adding compounds shown in 1) and/or (2) to (5) to photographic light-sensitive materials, coating performance is good, there is no adverse effect on photographic properties, and the material is resistant to various storage and usage conditions. Thus, a photographic material having excellent antistatic properties can be obtained. Further, for 100 parts by weight of at least one compound represented by general formula (1), at least one compound represented by general formulas (2) to (5) 2
When 0 to 500 parts by weight is used in combination, particularly preferable antistatic performance can be obtained and contamination of the conveying roller of an automatic developing machine and the developer can be prevented.

Applicant: Konishiroku Photo Industry Co., Ltd. 5. Subject of correction Procedural amendment

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one hydrophilic colloid layer and a photosensitive silver halide emulsion layer on a support, in which at least one layer has the following general formula (1).
Compounds represented by and/or general formulas (2), (3)
, (4), at least one of the compounds represented by (5)
A silver halide photographic material characterized by containing seeds. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is a higher alcohol having an alkyl group or alkenyl group having 8 to 22 carbon atoms, or an alkylphenol having an alkyl group having 4 to 12 carbon atoms. 1 to 1 ethylene oxide or/and propylene oxide
00 mol added residue, R_2 is OH or OR_1
It is. ) General formula (2) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (However, R_3 is an alkyl group or alkenyl group having 8 to 22 carbon atoms, A is ethylene or propylene, R_4 is a hydrogen atom or (AO)_nH, n is an integer from 1 to 50.) General formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_5 has 7 to 21 carbon atoms. alkyl or alkenyl group, R_6 is COR_5 or (AO)_nH
, x is an integer from 0 to 3. ) General formula (5) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_7 is (AO)_nH, A-N(R_4)_
2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, here y
is an integer from 1 to 3, and R_8 is N(R_4)_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. )