JPH04152337A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To uniformly apply a gelatin-contg. soln., etc., by incorporating specific compds. into silver halide emulsion layers or other hydrophilic colloidal layers. CONSTITUTION:The compds. of formula I or II are incorporated into the silver halide emulsion layers or the other hydrophilic colloidal layers. The compds. can be added in a 0.01 to 50g range per 1kg coating liquid as the amt. of the compds. to be used and the more preferable range is 0.05 to 5g. The compds. are preferably added by a method of adding the compds. in the form of a soln. prepd. by dissolving the compds. in water or methanol or other solvents which can be mixed with the water. The soln. is uniformly applied without comets and spills if the soln. is prepd. in such a manner. In the formulas I, II, R'; 8 to 32C alkyl group, alkenyl group, substd. alkyl group, substd. aryl group. R<2>, R<3>; a hydrogen atom, 6 to 32C alkyl group, substd. cycloalkyl group, substd. aryl group which are not simultaneously the hydrougen atom, m; number of 3 to 6, n; number of 1 to 50.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic material containing a new coating aid in a hydrophilic organic colloid coating layer, and more specifically to a silver halide photographic material containing a new coating aid in a hydrophilic organic colloid coating layer. The present invention relates to a silver halide photographic light-sensitive material containing a specific surfactant that can form a uniform coating film without causing such problems and can be coated at high speed.

(Prior Art) As is well known, photographic materials are provided with several layers of hydrophilic colloid (usually gelatin) on a support such as cellulose triacetate, polyethylene terephthalate, or paper. These layers have a number of functions such as an undercoat layer, an intermediate layer, a photosensitive layer, and a protective layer, and each layer contains various inorganic or organic additives in order to satisfy these functions.

In this way, general photographic materials are formed from many hydrophilic organic colloid layers, and during their production, these coating solutions must be coated in thin layers uniformly and at high speed without any coating failures such as cracking, repelling, or uneven coating. required to do so. As a coating method, a continuous and simultaneous multilayer coating method is often used in recent years.

The most difficult example of a coating process is the production of color photographic materials. In color photographic materials, many poorly water-soluble additives such as color couplers, ultraviolet absorbers, and optical brighteners are combined with high-boiling point organic solvents such as phthalate ester compounds and phosphate ester compounds, and ethyl acetate. dissolved in a co-solvent and dispersed in a solution of a hydrophilic organic colloid, in particular gelatin, in the presence of a surfactant (so-called emulsification),
It is used by being included in the hydrophilic organic colloid layer.

If a large amount of surfactant is used as an emulsifier in such an emulsion, it will become difficult to coat another hydrophilic organic colloid layer on top of the hydrophilic organic colloid layer.6 If the emulsifier is reduced, Aggregation of emulsion particles occurs and the photographic properties of the photographic material after coating become unstable.

Another example of the most difficult coating process is a curtain coating method in which a thin film of coating solution is applied by colliding with a support. (Special Publication No. 49-24133, No. 49-35447).

The most important issue with this curtain coating method is how quickly and stably the coating solution can be formed into a thin film.

Many improvements have been made to address this issue, most of which have focused on improving process equipment.

However, it has been found that improvements in equipment and equipment alone are not sufficient and that the results are significantly dependent on the physical properties of the coating liquid.

For these purposes, various anionic surfactants have been studied as coating aids for various coating solutions for photographic light-sensitive materials, and specific examples thereof include U.S. Pat. , 3.068, 1.01, 3,220,847, 3,415.649, 4
, No. 916,054, West German Patent No. 1,942,665,
Japanese Patent Publication No. 5950969 and recently Japanese Patent Publication No. 2-178
No. 649, No. 2178648, etc.

On the other hand, although there are few specific examples of nonionic surfactants as coating aids, for example,
Examples include sig sugar derivatives disclosed in US Pat. No. 24,722 and US Pat.

(Intelligence to be Solved by the Invention) However, when coating a colloid liquid such as gelatin on a colloid layer such as gelatin using these anionic surfactants as coating aids, calcium contained in gelatin Because the solubility of anionic surfactants is extremely reduced due to alkaline earth metal ions such as There was a drawback that the coating properties were significantly deteriorated.

Also, US Patent No. 38506 used to prevent static electricity.
Cationic surfactants disclosed in JP-A-57-146248, JP-A No. 57-146248, JP-A-557763, JP-A-53-
When using a cationic antistatic agent such as a cationic polymer disclosed in 92125, JP-A-5418728, etc. and an anionic surfactant as a coating agent in the same photosensitive material, in the same coating solution When added, there was a serious drawback in that the two would form an insoluble complex and cause comments.

On the other hand, regardless of the difference between coating aids and emulsification dispersion aids, even if they are added to a separate layer from the antistatic agent, both of them will dissolve into the processing solution when the photosensitive material is developed and will be insoluble in the processing solution. There was a problem that complexes were formed and uneven processing occurred.

In recent years, it has been suggested that the amount of washing water used during treatment be reduced from the standpoint of environmental conservation, water resources, cost, or simply making treatment equipment more compact. In addition, instead of a simple washing process with water, a method of reducing the amount of processing liquid by using a liquid containing various chemicals (for example, JP-A-57-8542, JP-A-57-8542;
-14834, 57-132146, 58-1
No. 8631, same 5! lt-184345, 57-1
No. 97540 and No. 5B-134636). In this way, when reducing the amount of water used for washing or using chemicals, the surfactant that flows out from the photosensitive material may remain unevenly on the coating surface and discolor over time, or the high boiling point solvent dispersed in the coating may It is known that the so-called sweating phenomenon caused by aggregation of couplers and the like is promoted.

In addition, in recent years, attempts have been made to reduce the amount of replenishment processing solution due to cost considerations, but in this case too, the proportion of surfactant accumulated in the processing solution increases, and the anionic surfactant that has been disclosed so far Continuing to process sensitive materials using agents has caused problems with the formation of tar-like insoluble matter.

Furthermore, in order to shorten the processing time, attempts were made to make the processing solution more concentrated, but this still had the same problems as above.

As part of shortening and simplifying the processing time, bleach accelerators (JP-A-59-95630, JP-A-59-95630, JP-A-59-95630, JP-A-59-95630)
7-192953, Japanese Patent Publication No. 5412056, U.S. Patent 4
, 552, 834) is known.

However, it is known that an insoluble complex is formed between these bleaching accelerators and the anionic surfactant released from the sensitive material, resulting in contamination of the processing solution.

In JP-A No. 54-98235, gelatin can contain alkaline earth metal ions such as calcium by using an alkaline earth metal salt of a certain anionic surfactant into which ethylene oxide is introduced. It is disclosed that excellent coating properties can be obtained. Although the use of alkaline earth metal salts of these anionic surfactants reduces coating failures such as repelling and provides somewhat better coating properties than conventional anionic surfactants, in recent years silver halide photosensitive materials have been It has not been possible to satisfy the high-speed coating properties required for the production of .

On the other hand, although nonionic surfactants do not have the above-mentioned problem of ionic complex formation, there are few that show excellent effects in terms of suitability for high-speed application for boat fishing, and some polysaccharide derivatives such as those mentioned above are known. It's just being told. However, these methods are not sufficient for the recent high-speed simultaneous multilayer coating method or the curtain coating method (thin film formation).

These problems may occur due to the properties of the surfactant itself used for each purpose, or due to interactions with other additives that they share. Therefore, in order to solve these problems, it is considered most preferable to improve the individual surfactants used, but in practice this often results in a loss of the intended performance and poses significant difficulties. Tomo.

(Object of the Invention) The first object of the present invention is to uniformly coat a gelatin-containing solution or other hydrophilic colloid solution onto a support such as film or paper or other photographic layer without any comments or repelling. An object of the present invention is to provide a photographic material coated with a photosensitive material.

Note that the comments refer to "Film Coating Theory J" by Deryagin et al. (B, M, Deryagin, S, M,
Levi, FilmCoating Dingheor
y+ The Focal Press, 1 9
6 4) P.

As described in detail in 183, it is a phenomenon in which minute amounts of oil particles, mineral oil particles, hydrophobic liquids, and solids contained in the coating solution form a core that is locally uncoated, including the surrounding area. Also, repellency refers to a phenomenon in which a coating solution does not spread sufficiently due mainly to surface tension, resulting in some areas not being coated. The second object of the present invention is to provide a method for forming a stable thin film in a curtain coating method and coating at high speed. An object of the present invention is to provide a photographic material that does not cause contamination.

(Means for Solving the Problems) These objects of the present invention are to contain a compound represented by the following formula [1] or (If) in a silver halide emulsion layer or other hydrophilic colloid layer. This was achieved by

R1 NRCQ (C)ln,C)ItO(CH2CHCHHz
O') llH(I[) 0[(OH In the formula, R1 represents an alkyl group having 8 to 32 carbon atoms, an alkenyl group, a substituted alkyl group, a substituted aryl group, Rt
, R2 each represents a hydrogen atom, an alkyl group having 6 to 32 carbon atoms, a substituted cycloalkyl group, or a substituted aryl group, and R2 and R3 are not hydrogen atoms at the same time. m represents a number from 3 to 6, and n represents a number from 1 to 50.

The present invention will be explained in more detail below. - Preferable examples of R1 in the formula (H include an alkyl group having 8 to 16 carbon atoms and R'0(Ctlz)i (R' is a group having 6 to 16 carbon atoms)
18 straight-chain or branched alkyl groups). R'
And a specific example of R' is n-C@H+t + C
JJHCHz, n-C+oHz+, n
-C6nts +C,H.

C@H+tCHCH2+ n-CItHza + n-
Examples include C+bHzs +CbH+5 C1°Hz+CHCHz.

Preferred examples of RZ and R3 in general 2CJ+t (II) are both alkyl groups having 6 to 12 carbon atoms. As a specific example of R2R3, n-CJ+ff+ n-CJ+y +CJq
CJICtlz, n-C+oHz+ + n-CI
Examples of tHza, etc. are C and H.

I can do it.

The preferable number of m in general formulas (1) and (II) is 4
or 5, and the number of n is 1 to 10, particularly preferably 1 to 10.
It is 5.

Next, preferred specific examples of the compounds represented by the general formulas [1] and [n) used in the present invention will be shown, but the present invention is not limited thereto.

(Compound) 1°C,1(JHCO(C)I), CF[ZO(CHzCHCLO
) 2HH OH 2゜C+ JzsNHCO (C8) 4c) ItO (CHz
(lJIcHzo) 3HH OH 3゜4゜6゜C+! HzsO(CHz) 3NHCO(CH)s
cH*o(CHzCHCHzO) JH OH 9°C+ IIH3? NHCO(CH) 4clIzo(C
Hz (JICHzO) +. HH OH 10゜OH OH 11゜OH H 12゜13゜CsH,jcHc)120(C)12), NHCO(C
H), CH20(CH2CHCH,O),. ■CbH
+z CH CH 14゜C4HqCHO(CFIz)JHCO(C)ri4ct(
zO(C)lzc)ic)IzO)z)IJs CH CH 15°CH CH Synthesis examples of these compounds used in the present invention are shown below.

Synthesis Example 1 (Synthesis of Compound Example 1) Octyl-N-gluconylamine 38.77 g (0.3 mol) of octylamine and 500 ml of methanol are placed in a No. 11 three-way flask and dissolved. δ-Gluconolactone 5 by keeping the internal temperature at 50°C
3.44 g (0.3 mol) are added little by little while stirring. After the addition was completed, the mixture was reacted for 5 hours under methanol reflux. When allowed to cool to room temperature, crystals precipitate. The crystals were taken out and recrystallized from a mixed solution of 1000 d of methanol/500 d of ethanol. It was confirmed by NMR that it was the desired product.

112 ↓ Octyl-N-gluconylamine 30.74g (001
mol), dimethylformamide (DMF) 10 (1!,
2 g (0.05 mol) of Na0) is placed in a 300-paper Mitsuro flask and stirred at 90 to 100'C until one Na0) grain becomes a scum. D under reduced pressure below 80℃
After distilling off the MF, add 80% of DMF to 120%
Glycidol 14.8 under stirring while keeping at ~130°C
g (0.2 mol) is added dropwise. The reaction was carried out at the same temperature for 6 hours with stirring. Unreacted glycidol is not observed. After cooling, neutralize with concentrated hydrochloric acid. After distilling off the solvent under reduced pressure, methanol (100%) is added, the mixture is melted again, activated carbon is added, heat decolorized, filtered, the solvent is concentrated under reduced pressure, and further washed with acetone to obtain a pale brown solid. Confirmed to be the desired product by IR and NMR (however, it also contains some reactants with secondary OH groups due to the reaction of glycidol), transparently dissolved in water, and has a surface tension (1%) of 28 dyne/ It was cm.

Synthesis Example-2 (Synthesis of Compound Example-4) 2-ethylhexyloxypropylamine 56°02g
(0.3 mol) and methanol 600Id were placed in 12 three-meter flasks and dissolved. 53.44g (0.3 mol) of δ-gluconolactone while keeping the internal temperature at 50°C
Add a little at a time while stirring. After the addition was completed, the mixture was reacted for 5 hours under methanol reflux. A solid is obtained by distilling off methanol under reduced pressure. It was recrystallized from a mixed solution of 1300 d of acetonitrile/400 d of ethanol. Yield 40g, NM
It was confirmed from R that it was the desired product.

Old ``31 Ei Example 2'' - The addition reaction of glycidol was carried out in the same manner as in Synthesis Example 1 to obtain the desired product.

Synthesis Example-3 (Synthesis of Compound Example-10) 36 g of sodium hydride in 2-dihexylpropane dry DMS0800d
(2.0 mol) was added to the slurry containing DMSO20
66.1 g (1.0 mol) of malononitrile dissolved in Oaf was slowly added under stirring and cooling with water. After completion, stirring was continued for 20 minutes, and then 330% of hexyl bromide was added. i
g (2.0 mol) was added dropwise under ice cooling (20°C
After completion of the reaction, the reaction mixture was stirred for 2 hours at 30° C. or below and then for 4 hours at 50° C. The reaction solution was poured into 3000 Mi of ice water and stirred. Next, 20,001 dl of ethyl acetate was added to extract the oil, and the separated ethyl acetate layer was washed twice with water. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off to obtain a yellow oily substance. The oily substance was distilled under reduced pressure to obtain 181 g of the desired product as a colorless oil. (boiling point, 153-b-dihexylbroban)
-Diamine 2.2-dihexylpropanedinitrile 1
Dissolve 80゜5g (0.77 mol) in 320d of ethanol, add about 5g of Raney nickel (toluene dispersion), and heat in an autoclave at hydrogen pressure toOkg/rrf, 10
Catalytic reduction was performed at 0° for 66 hours. The catalyst was removed and ethanol was distilled off to obtain an oily substance. The oily substance was distilled under reduced pressure to obtain 119 g of the desired product as a colorless oil.

(Boiling point, 153-160'C/4m+iHg).

2.2-dihexylpropane-1.3-diamine24.
24 g (0.1 mol) and 35.63 g (0.2 mol) of 1.5-D-gluconolactone were dissolved in 600 g of methanol.
The reaction was carried out under reflux for 6 hours. When allowed to cool to room temperature, crystals precipitate. This was collected by filtration and recrystallized from methanol. It was confirmed by NMR that it was the desired product.

The melting point was 180°C and the yield was 30g.

The addition reaction of human glycidol of Mu-0 was carried out in the same manner as in Synthesis Example 1 to obtain the desired product.

The nonionic surfactant represented by the general formula (1) or [II] used in the present invention is extremely excellent as a coating aid for coating liquids using the above-mentioned high-speed simultaneous multilayer coating method for photography or curtain coating method. I found out. In other words, it was found that uniform, high-speed simultaneous coating was possible without comments or repelling. Furthermore, general formula [I] and CI[ used in the present invention
] It has also been found that a photographic film containing a compound represented by the following has characteristics such as being able to prevent the generation of contaminants in a processing solution. The reason for these effects is presumed to be that the compound of the present invention has many hydroxyl groups in its molecule, resulting in interactions between hydroxyl groups, particularly the cooperative effect of sugar hydroxyl groups and glycerol hydroxyl groups. .

In the present invention, the compounds represented by formulas CI) and CU are added to a hydrophilic organic colloid coating solution and used as a coating aid, and the amount used is 0.01 per coating solution.
It can be added in the range of ~50g, but preferably 0.05~
5g is appropriate.

As for the method of addition, it is preferable to add the compound as a solution in a solvent mixed with water, methanol, or other water.

The surfactant may be added to the coating solution for any photographic layer constituting the photographic light-sensitive material, regardless of whether the layer is a photosensitive layer or a non-photosensitive layer.

In the photographic material of the present invention, an extremely uniform coating film of hydrophilic colloid is formed not only at low speeds but also at high speeds by adding the compound represented by the above-mentioned formula.

In other words, uneven coating, comments on the coating film, and repellency do not occur.

The present invention is particularly useful as a coating aid when a photosensitive material contains lipophilic substances such as couplers, alkylhydroquinones, ultraviolet absorbers, sensitizing dyes, and hydrophobic vinyl polymers.

That is, a solution obtained by dissolving these lipophilic substances in a high-boiling point poorly water-soluble organic solvent is finely and stably dispersed in a hydrophilic colloid aqueous solution in the presence of a surfactant of the above-mentioned formula, and this is directly applied. It can be used as a liquid, or it can be added to a coating liquid such as a photographic emulsion.

On the other hand, it is also effective when preparing an aqueous dispersion of a hydrophobic vinyl polymer. That is, a hydrophobic vinyl monomer is emulsified in an aqueous solution containing a surfactant according to the present invention, and then a polymerization initiator is added and polymerized to obtain a stable aqueous dispersion with fine particle size.

As the hydrophilic organic colloid in the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Journal of the Photographic Society, Japan (Bull).

Soc, Sci, Phot, Japan, )N
Enzyme-treated gelatin as described in CL l 6, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used.

The hydrophilic organic colloid layer in the present invention is a photographic coating layer containing the above-mentioned hydrophilic organic colloid, especially gelatin, as a binder, such as a silver halide emulsion layer, a surface protection layer, a filter layer, an intermediate layer, etc. , antihalation layer,
Examples include a static prevention layer, a subbing layer, and a backing layer.

Since the compound of the present invention has high solubilizing power and surface activity, it is preferably used for coating a hydrophilic organic colloid layer in which a poorly water-soluble photographic additive is dissolved and dispersed using a high boiling point organic solvent. .

Various silver halides can be used in the silver halide emulsion layer according to the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

Silver iodobromide containing 2 to 20 mol % silver iodide and silver chlorobromide containing 10 to 50 mol % silver bromide are preferred. There are no limitations on the crystal form, crystal structure, grain size, grain size distribution, etc. of the silver halide grains. Silver halide crystals may be normal crystals or twin crystals, and may be hexahedral, octahedral, or tetradecahedral. The grains may be tabular grains having a thickness of 0.5 microns or less, a diameter of at least 0.6 microns, and an average aspect ratio of 5 or more, as described in Research Disclosure 22534.

The crystal structure may be similar, the inside and outside may have different compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding, and various crystal structures may be used. It may also consist of a mixture of particles in crystalline form. Further, the latent image is mainly formed on the surface of the particle, but may be formed inside the particle.

The grain size of the silver halide may be fine grains of 1 micron or less, or dog-sized grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

These silver halide grains can be produced by known methods commonly used in the art.

The silver halide emulsion is subjected to conventional chemical sensitization, that is,
Sensitization can be achieved by sulfur sensitization, noble metal sensitization, or a combination thereof. Furthermore, the silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Dyes that can be advantageously used in the present invention include methine dyes and styryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxonol, and hemioxonol, and one type or a combination of two or more types can be used.

Examples of poorly water-soluble photographic additives used in the present invention include oil-soluble color couplers, antioxidants used to prevent color fogging or color mixing, and antifading agents (e.g., alkylhydroquinones, alkylphenols, chromans, etc.). , coumarons, etc.), hardeners, oil-soluble filter dyes, oil-soluble ultraviolet absorbers, DIR compounds (e.g., DIR/
\hydroquinones, colorless DIR compounds, etc.), developers, dye developers, DRR compounds, DDR couplers, etc.

As the oil-soluble color coupler, benzoylacetanilide-based, pivaloylacetanilide-based, pyrazolone-based, cyanoacetyl-based, phenol-based, and naphthol-based compounds can be used. Representative examples of these are U.S. Patent Nos. 2,875,057, 3,408,194, and
No. 582322, No. 3891445, No. 260078
No. 8, No. 3062653, No. 3311476, No. 3
51, No. 9429, No. 3558319, No. 36155
No. 06, No. 3834908, No. 2369929, No. 2474293, No. 2895826, No. 35913
No. 83, No. 3227544, No. 3790384, etc.

Examples of high-boiling organic solvents used in the present invention include phthalic acid alkyl esters (dibutyl phthalate, octyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.). )
, citric acid esters (eg, acetyl tributyl citrate), benzoic acid esters (eg, octyl benzoate), alkyl amides (eg, diethyl laurylamide), and the like.

In addition, the hydrophilic colloid coating solution used in the present invention may contain stabilizers, hardeners, dyes, matting agents, photosensitive silver halide particles, other surfactants, polymer latex, fluorescent brighteners, and others. It can contain various additives useful for photographic materials.

Other surfactants to be used in combination with this surfactant invented by Shiraki As the active agent, a chiion type surfactant is preferable.

Regarding the above additives, product licensing
Index Magazine Vol. 92, pp. 107-110 (1971, 1
February), Research Disclosure 15162 (19
(November 1976) and No. 17643 (December 1978).

When the hydrophilic organic colloid coating layer containing the compound of the present invention contains a silver halide emulsion, even if the coating layer has a water permeable relationship with the silver halide emulsion layer,
Alternatively, unlike the back layer, it may not be in a water permeable relationship with silver halide.

The invention can also be used for single layer or simultaneous multilayer coatings that do not contain any silver halide emulsion layers. When performing simultaneous multilayer coating, the compound of the present invention may be contained in all coating solutions, but preferably when added to the top layer or the layer adjacent thereto, the reduction in coating failures and the improvement in coating speed are remarkable. . Coating repellency is also reduced when the coating layer containing the compound of the present invention is in a cooled and set state and a coating layer not containing the compound of the present invention is further provided thereon.

When applying simultaneous multilayer coating, U.S. Patent No. 2,761°417
Hopper coating described in No. 3. 508. 947, or other coating methods as described in Research Disclosure 17644 (December 1978).

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these.

Example 1 1 kg of silver chlorobromide emulsion (containing 100 g of gelatin per mole of silver halide) grain-formed and ripened in a conventional manner
was diluted three times with a 10% aqueous gelatin solution, and 2 g of saponin was added per 1 kg of this emulsion solution. Separately from this emulsion solution, a 5% aqueous gelatin solution was prepared and added to this
An emulsion obtained by dispersing hexyl phosphate in gelatin (average particle size 0.9μ) was added as tri-n-hexyl phosphate to make a 5% gelatin aqueous solution at 18cc/1kg to make a solution. Ta. This liquid was sufficiently divided into equal parts, and 2.0 g/kg of a coating aid was added to each part to form a coating liquid for a surface protective layer.

The surface tension of this surface protective layer coating solution is determined by the Wilhelmy hanging plate method (e.g. E, Matijevia surface and colloid science).
d Sc:ence')v.

1, 1 p, 124-128, Wiley-1nt
ersscience (1969)).

On the other hand, two layers of the emulsion solution and the coating solution for the surface protective layer were simultaneously coated at a coating speed of 100 m/min onto a cellulose triacetate support provided with an undercoat layer using a multi-slide hopper type coating device.Sample-(1) - (4) were prepared, and the number of /"l fish per square meter was determined for each sample. The degree of roller contamination was evaluated by the following method.

The results obtained are shown in Table 1.

Measurement of degree of roller contamination A sample coated with an emulsion layer and a surface protective layer was heated at 30°5ao.
It was cut into a 17.1cm x 17.1cm square. After uniform exposure so that the optical density after processing is 1.0, an automatic processing machine (equipped with a silicone roller conveyor) (developer = Fuji Photo Film RD-II 35°C, fixing bath = Fuji Photo Film 50 sheets were continuously developed in a Fuji-F (35° C., consisting of 3 baths including a water washing bath).

After thoroughly drying the water-washed squeeze roller, the appearance of streak-like density unevenness at the tip of the 51st sample was examined.

The degree of roller contamination was evaluated according to the following four-level criteria. (
The degree of contamination is high (the density unevenness increases) A: No density unevenness is observed.

B: Slight density unevenness occurs.

C: Considerable density unevenness occurs.

D: Significant density unevenness occurs.

Table 1 Comparative compound A Comparative compound B CBH, tcONH (C) I), CHzOHH Comparative compound! ! ! 7IC H As is clear from Table 1, the samples (4 to 6) using the compounds of the present invention have a small number of repellents and a small degree of dyeing on the roller.

Example-2 1 kg of 7% gelatin aqueous solution, 0.6 g of potassium polyvinylbenzenesulfonate and coating aid 2. A coating solution for a surface protective layer to which Og was added was prepared for each of the comparative compound and the compound of the present invention.

These coating solutions were used to form a curtain film using an extrusion type curtain coating apparatus disclosed in Japanese Patent Application Laid-Open No. 55-73365, and the minimum flow rate (Q) at which the film could be formed was measured.

In addition, the above coating liquid was applied onto a polyethylene terephthalate film using this curtain coating apparatus, and the limit coating speed was investigated. These results are shown in Table 2.

Table 2 *Q: Curtain # (height 50
mm).

**Limit speed: Q=3. When the film height is 0cc/c-5ec and the film height is 50+++, the speed is the limit at which normal coating cannot be performed due to air entrainment.

Comparative Compound A Comparative Compound C H Comparative Compound D C,6H: +jO(CHzCHzO) +. As can be seen from Table 2, the Q of comparative samples 7, 8, and 9 is 2.
1.1. 5.2.3, whereas sample 1 of the present invention
It can be seen that 0.11.12 is effective in forming a curtain film even with a small Q of 0.9.0°7.0.8, and is effective in forming a thin curtain film. It can also be seen that the critical speed is clearly superior to that of the comparative compounds.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide emulsion layer or other hydrophilic colloid layer contains the following general compounds. A silver halide photographic material containing a compound represented by formula [I] or [II]. [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 is an alkyl group with 8 to 32 carbon atoms, alkenyl group, substituted alkyl group, substituted Represents an aryl group. R^
2 and R^3 each represent a hydrogen atom, an alkyl group having 6 to 32 carbon atoms, a substituted cycloalkyl group, or a substituted aryl group, and R^2 and R^3 are not hydrogen atoms at the same time. m represents a number from 3 to 6, and n represents a number from 1 to 50.