JPS6368836A - Silver halide photographic sensitive material containing novel surfactant - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of uniformly coating, without effecting undesirable influence to photographic characteristics by incorporating a specific surfactant having two lipohilic groups to the titled material. CONSTITUTION:The titled material comprises at least one layer of a hydrophilic colloid layer on a substrate body. The surfactant which has a satd. or an unsatd. hydrocarbon chain having >=4 C an branched chain and/or a partical structure shown by formula I is incorporated to at least one layer of the hydrophilic colloid layer or said layer contg. a polymer latex. In the formula I, R1 and R2 are each 4-25C a satd. or an unsatd. hydrocarbon group, A is a trivalent binding group. Thus, the titled material which enables to form the uniform coating film of the hydrophilic colloid layer and affects no undesirable influence to the photographic characteristics is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic material containing a novel surfactant, and more specifically, it is free from cissing, unevenness, etc. The present invention relates to a silver halide photographic material which not only can be uniformly coated but also serves as a good dispersant for additives, particularly polymer latex, and contains a novel surfactant that does not adversely affect photographic properties.

[Background of the Invention] Generally, a photographic light-sensitive material has a plurality of photographic constituent layers containing hydrophilic colloids provided on a photographic support. These photographic constituent layers have various functions such as an undercoat layer, an intermediate layer, a photosensitive layer, and a surface protective layer. Therefore, when producing photographic materials, gelatin etc. are often used on the support. A plurality of different photographic constituent layers containing parent tree colloids may be coated simultaneously in layers, and in this case, the coating solution is coated uniformly, quickly, and thinly without causing coating failures such as repelling. Layer application is required. In order to satisfy this requirement, attempts have been made to add surfactants to coating liquids, and many compounds are known as such surfactants. -50
969, JP-A-51-3219, Belgian patent 70B3
Part of it is described in 47, 723890, etc.

Also, organic solvents for hydrophobic photographic additives such as couplers, ultraviolet absorbers, and optical brighteners, and hydrophobic synthetic polymers such as acrylic esters (hereinafter referred to as polymer latex).

) Also when applying a hydrophilic colloid solution containing a dispersion, a surfactant is indispensable as a dispersant.

However, surfactants used in photographic light-sensitive materials have good processing properties that require photographic properties such as photographic sensitivity, fog, and gradation, as well as rapid processing properties such as speed of development (i.e., there is no wetting on the film surface). It is necessary that the surfactant has no adverse effect on the surface (e.g., good surface area and no adhesion of bubbles, etc.), but many of the surfactants used conventionally are It is undesirable in terms of wetting, and when a surfactant is used as a dispersant for photographic additives, it is undesirable because it often generates bubbles, cissing, etc. In particular, when adding polymer latex to a hydrophilic colloid layer to improve the physical properties of the film, it is necessary to consider the scratch strength, dimensional stability, flexibility, etc. of the hydrophilic colloid layer. 852,38
No. 6, Special Publication No. 57-9051, Japanese Patent Publication No. 57-2000
Examples thereof are disclosed in No. 31, etc. Polymer latex tends to aggregate in seratin, and there is always concern that dispersion stability and applicability will be affected, and it has not been fully satisfactory. Therefore, when a surfactant is added to a photographic coating solution, it does not result in uniform coating of the photographic coating solution, and uneven development occurs during development, which is not desirable, and improvements are desired.

Therefore, the present inventors conducted research on surfactants while taking into account the problems and drawbacks mentioned above, and found that photographic properties could be improved by using a new surfactant that had a kind of exchangeable basis. It has been discovered that the above problems can be solved without causing any adverse effects. Therefore, the present invention has been completed based on this knowledge.

[Object of the Invention] Therefore, the first object of the present invention is to provide a coating aid or a lipophilic photographic additive that does not substantially adversely affect photographic properties such as photographic sensitivity, fog, gradation, and development speed. An object of the present invention is to provide a silver halide photosensitive material containing a dispersant.

A second object of the present invention is to provide a silver halide photographic sensitizer in which a polymer latex is uniformly coated in a hydrophilic colloid without agglomeration, and the physical properties of the film such as tilit strength, dimensional stability, and flexibility are improved. The purpose is to provide materials.

A third object of the present invention is to provide a silver halide photographic material in which a hydrophilic colloid layer made of a hydrophilic colloid such as a binder is uniformly coated on a support.

A fourth object of the present invention is to obtain stable photographic processing characteristics that have good wettability with photographic processing solutions, do not generate bubbles even when developing automatically at high speeds, and are uniform. The object of the present invention is to provide a silver halide photographic light-sensitive material that can be used.

[Structure of the Invention] The above object of the present invention was achieved by using a surfactant having two lipophilic groups as a new surfactant. That is, the present invention provides a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, in which at least one of the hydrophilic colloid layer or the hydrophilic colloid layer containing polymer latex has a carbon number of 4 or more. This is a silver halide photographic material characterized by containing a surfactant having a branched saturated or unsaturated hydrocarbon chain and/or a partial structure represented by the general formula [1].

General formula [■ R2 R, -A- R,, R2 represents a saturated or unsaturated hydrocarbon group having 4 to 25 carbon atoms, and A represents a trivalent linking group.

More specifically, the surfactant having a partial structure represented by the general formula [I] is preferably one represented by the general formula [n].

General formula [+1] R2 ■ Rl +A ) -(-B-+-n0 In the formula, R,, R2 represents a saturated or unsaturated hydrocarbon group having 4 to 25 carbon atoms, and A is trivalent or tetravalent. represents a connecting group.B represents a divalent group.

Furthermore, D represents a hydrogen atom, a hydrophilic group, or an alkyl group, alkenyl group, aryl group, or acyl group having 1 to 25 carbon atoms. n represents an integer from 0 to 50.

Examples include SO2N, CH2Coo-, etc.

The divalent group represented by B is an alkyl group having 1 to 25 carbon atoms, an oxyalkylene group (for example, an oxyethylene group,
Preferred examples include oxypropylene group, 2-hydroxyoxypropylene group, 2-methoxy-oxypropylene group, oxybutylene group, and α-phenyloxyethylene group. )
, oxyarylene group, etc.

The hydrophilic group represented by D is -C00M, -303M,
-0303M.

Anionic groups such as -OP (OH)2 (M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, lower alkylammonium, etc.) (R3, R, t
, Rs is preferably an alkyl group, alkenyl group, or phenyl group having 1 to 25 carbon atoms, and X is OH, C1l, Br, l
Examples include XNO3, polyhydric carboxylic acid, and the like. ), amphoteric groups such as (℃ is 1-6) or hydrogen atom, carbon number 1-2
Examples include groups having a nonionic group such as a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, and an acyl group.

D is preferably an anionic group, an amphoteric group, or a nonionic group, and when D is a nonionic group, it is preferably used in combination with an anionic surfactant.

Next, specific compounds of the surfactant of the present invention will be listed, but those listed here are particularly preferred in the present invention, and the present invention is not limited thereto.

2, CaH+y C6H+7CH5O3Na 5, (:4)19 05H+7CI(CLCHCLSO3NaOH", C(l)117 C6H17CONIj12CH20SOJa9,
C8H+t C011□, C6H17S to coNco2an2coo
O2NCH2Ct12082COONaCzHs (Hereinafter, blank) The surfactant of the present invention has a concentration of 0.00% per Ikg of various photographic coating solutions.
It can be added in the range of 0.01 to 50 g, but usually 0.05 g.
~5g is appropriate. As for the addition method, it is preferable to add it as a solution in water or a solvent mixed with methanol or other water.

The surfactant of the present invention can be used in the coating solution of any of the hydrophilic colloid layers such as the undercoat layer, intermediate layer, photosensitive layer, and surface protective layer, which are photographic constituent layers constituting the silver halide photographic light-sensitive material of the present invention. It does not matter whether the hydrophilic colloid layer is a photosensitive layer or a non-photosensitive layer.

The surfactant of the present invention is useful as a dispersant when lipophilic substances such as couplers, alkylhydroquinones, ultraviolet absorbers, and sensitizing dyes are incorporated into photographic materials.

The lipophilic substance can be obtained by dissolving the solution in a high boiling point, poorly water-soluble organic solvent, finely and stably dispersed in an aqueous hydrophilic colloid solution in the presence of the surfactant of the present invention, and then used directly as a coating solution. , it can be further added to a coating solution such as a photographic emulsion.

Even when the surfactant of the present invention was added to a photographic emulsion in a large amount, no adverse effect on photographic properties was observed.

The surfactant of the present invention can also be used in combination with other anionic, cationic, nonionic, or amphoteric surfactants.

In this case, these surfactants may be added to the same layer or separate layers among the plurality of hydrophilic colloid layers. Examples of other surfactants that can be used in combination include those described in Ryohei Oda and Hiroshi Teramura, Synthesis of Surfactants and Their Applications (Maki Shoten 1984 edition).

The surfactant of the present invention can be added to various hydrophilic colloid coating compositions commonly used in the photographic field.

Examples of such hydrophilic colloids include the most typical gelatin, as well as cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, synthetic polymers such as polyacrylamide, etc. alone or in mixtures.

In the silver halide photographic material of the present invention, the surfactant of the present invention is present in a hydrophilic colloid together with the polymer latex. Such a polymer latex can be easily produced by redispersing a polymer obtained by a known emulsion polymerization method, solution polymerization method, or bulk polymerization method. Among these polymerization methods, the emulsion polymerization method is preferred.

In this emulsion polymerization method, the reaction temperature is 20 to 180°C.
, more preferably at 40 to 100° C., water, 10 to 50% by weight of a hydrophobic vinyl compound based on the water, and a polymerization initiator of 0.05 to 5% by weight based on the amount of water. 0.1～
This can be done using 20% by weight of emulsifier.

At this time, the surfactant of the present invention can be present as a dispersion stabilizer, and the polymerization initiator, concentration, reaction temperature, reaction time, etc. can be varied widely and arbitrarily depending on the purpose.

When the surfactant of the present invention is present during polymerization, the surfactant of Akira Kiki may be used in part or all of the amount added to the photographic coating solution.

Although the emulsifier can generally be synthesized without using it, it is preferable to use it in view of the stability of the resulting polymer latex over time, its compatibility with hydrophilic colloids, etc.

When polymerizing the polymer latex of the present invention, other anionic, cationic, amphoteric, or nonionic surfactants or emulsifiers such as water-soluble polymers may be used instead of or in combination with the surfactant of the present invention. Can be used.

Examples of the polymerization initiator used in the polymerization method of the polymer latex of the present invention include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate;
Water-soluble azo compounds such as sodium azobis-4-cyanovalerate and 2,2'-azobis(2-amidinopropane) hydrochlorides, and hydrogen peroxide can be used.

The molecular weight of the polymer latex of the present invention is 2,000 to 1
,000,000 is preferred, more preferably 5,00
0 to 500,000. The particle size is preferably 0.01 to 1 μm, more preferably 0.01 to 0.5 μm.

The polymer used to obtain the polymer latex is not particularly limited as long as it is a polymerizable ethylene monomer, but hydrophobic vinyl monomers are preferred. Examples of such hydrophobic vinyl esters include acrylic esters, methacrylic esters, vinyl acetate,
Styrene, vinyl chloride, vinylidene chloride, butadiene, etc. are preferably used.

The acrylic esters include medyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, 5ec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate,
Cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, hensyl acrylate, methoxypencyl acrylate, 2-
Chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate,
3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxy Polyethylene glycol acrylate (number of added moles n-9),
1-bromo-2-methoxyethyl acrylate, 1,1
-cyclo-2-ethoxyethyl acrylate and the like.

Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, lopropyl methacrylate, isopropyl methacrylate, loobyl methacrylate, isobutyl methacrylate, 5e
c-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate-1, hensyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulpobrobyl methacrylate, N-ethyl-N-phenylamino Ethyl methacrylate, 2-
(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyedyl methacrylate,
Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxyethyl methacrylate, triethylene glycol methacrylate,
Dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-
Acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate,
2-(2-methoxyethoxy)ethyl methacrylate-I-
, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added nJ), allyl methacrylate, methacrylic acid dimethylaminoethylmethacrylate salt, etc. I can list the following.

The amount of the polymer latex of the present invention is preferably 80% by weight or less, more preferably 5% by weight based on the hydrophilic colloid, and the coating rate is about 0% per m2 of hydrophilic colloid layer.
01-50g is preferable, more preferably 0.1-1.
It is 0g.

Hydrophilic colloids forming the hydrophilic colloid layer of the photographic light-sensitive material of the present invention include, in addition to the most typical gelatin, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, synthetic polymers such as polyacrylamide, etc. alone or in mixtures. Can be mentioned. Water-insoluble polymers such as polyacyl acrylates or polyalkyl methacrylates may also be dispersed in such hydrophilic colloids.

The photographic material of the present invention includes silver chloride, silver bromide, silver iodide,
Silver halides used in ordinary photographic materials, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are used.

In addition to silver halide photographic emulsions, there are also direct positive photographic emulsions that have silver halide grains whose surfaces have been pre-diffuted with light, reducing substances, noble metal salts, etc., and internal latent image emulsions that produce positive images through surface development. Type photographic emulsions can also be used.

The silver halide emulsion may be chemically sensitized with a sulfur compound, selenium compound, noble metal compound, etc., or fractionally sensitized with a sensitizing dye in a conventional manner.

The coating liquid used to form the photographic constituent layers according to the present invention includes inorganic hardeners such as chromium alum, chromium acetate, etc., formaldehyde, mucochromic acid, active halogen compounds, active vinyl compounds, ethyleneimide compounds, etc. It may contain various photographic hardeners such as organic hardeners.

The photographic light-sensitive material of the present invention may contain various emulsion stabilizers such as azaindene compounds and phenylmercaptotetrazole, antifoggants, and the like. In addition, various additives necessary for obtaining photographic materials, such as surface-modifying detergents such as silicones, fluorine-containing compounds, and fatty acid esters,
Color photosensitive dyes may contain various color couplers, filter dyes, dyes such as anti-irradiation dyes, plasticizers, etc.

As the silver halide photographic light-sensitive material according to the present invention, ordinary black-and-white silver halide photographic light-sensitive materials (for example, X-ray
black-and-white photosensitive materials for printing, black-and-white photosensitive materials for printing, etc.) Ordinary multilayer color photographic materials (e.g., color rehearsal film, color negative film, color positive film, etc.),
Various photographic materials may be mentioned.

Supports for these photographic materials include cellulose ester,
Plastic films such as polycarbonate and polyethylene terephthalate, paper, or glass are used.

[Example] The present invention will be explained in more detail by showing examples below.
This is an example, and the present invention is not limited thereto. Note that all percentages are by weight unless otherwise specified.

Example 1 Silver chlorobromide emulsion containing 7% gelatin and 5% silver halide (
0.2 g of Exemplified Compound 2 was added to Emulsion A (silver chloride 50 mol %) per 1 kg of the emulsion. This photographic emulsion was coated on baryta paper by a dip method at a coating speed of 50 m/min and cooled and set. A gelatin solution containing 1 g of each of Exemplified Compounds 2, 4, 8, 14, and 29 in 1 kg of a 2°-linked gelatin solution was applied thereon as a protective layer, and dried after cooling and setting (Sample No. 01). Also, in the emulsion A, 1
150 polyethyl acrylate 1-latex containing 0.2 g of Exemplified Compound 1 and a particle size of 0.05 μm per kg.
g (solid content: 20% by weight) were added. This photographic emulsion was coated on baryta paper by a dip method at a coating speed of 50 m7, and cooled and set. On top of this, as a protective layer, exemplified compound 2.4°6 was added in 1 kg of 2.5% gelatin solution.
．． 8, 14.29 and 150 g of polyethyl acrylate latex with a particle size of 0.805 μm.
A gelatin solution containing (solid content 20% by weight) was coated, cooled and then dried (Sample No. 2).

There were no bubbles or cissing in the emulsion layer and protective layer of Samples No. 011, No. 2, and Samples No. 1 and 2.
The coating speed was 70 m/min, and the coating speed was 50 m/min for sample No. 2.
Uniform coating was possible at a coating speed of m/min. Furthermore, when these samples were developed with a normal metol-hytroquinone developer, no bubbles were generated during development, and even images were obtained, with no adverse effects on photographic properties (sensitivity, gamma, fog). There wasn't.

Example 2 A high-sensitivity, high-contrast emulsion containing 6% gelatin and 6% silver iodobromide (silver iodide 1.5 mol%) was prepared. To this photographic emulsion, 0.01 g of sodium dodecylhenzenesulfonate and Exemplary Compounds 2 and 21 were added to
．． It was added as a 2% aqueous solution so that it was contained in a range of 5 g, and samples with different amounts were created. Furthermore, 150 g (solid content: 20% by weight) of polyethyl acrylate latex was added to the emulsion containing Exemplified Compound 2. These emulsions were each coated on a cellulose triacetate support having an undercoat layer and dried. Exemplary compound 21 as shown in Table 1
It can be seen that the number of repellents is greatly reduced by adding . Furthermore, it can be seen that as the amount of Exemplified Compound 2 increases, the number of repellents decreases significantly even if the polymer latex is contained. Furthermore, even when using a high-sensitivity, high-contrast emulsion, it was possible to obtain a photographic material having good photographic properties with no or very little occurrence of fog.

Example 3 Negative photographic emulsion containing 7% gelatin and 8% silver iodobromide (silver iodide 7 mol%) 0.15 g saponin and polyoxyethylene nonylphenyl ether (chain length of polyoxyethylene: 15 ), a photographic emulsion containing 06g;
A surface protective layer containing Compound 4.11 or 15 according to the present invention and a known surfactant as shown below per 1 kg of a 7% aqueous gelatin solution was applied to a triacetyl cellulose support undercoated to a dry film thickness. are 5μ and 1μ respectively
They were applied simultaneously using a multi-layer coating method to achieve the desired results, and dried after cooling and setting. The surface protective layer of each photographic film sample obtained was inspected and the number of spots (repellents) where the coating was uneven was counted.

Further, a commercially available phenidone-hydroquinone developer was dropped onto each sample placed horizontally, and the contact angle was measured using a contact angle measuring device (Goniometer Model G-1 manufactured by Elma). If the value of this contact angle is large, when a photographic film is placed in a developing solution, it is difficult to wet the film, resulting in adhesion of bubbles and uneven development. Therefore, it is desirable that the contact angle value is small. Table 2 shows these results.

As is clear from Table 2, when the method of the present invention is carried out, the contact angle is small, and moreover, almost no repellency is observed. On the other hand, typical anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate reduce the repellency number, but the contact angle is large and the film surface easily repels water and developer, resulting in uneven development. Furthermore, polyoxyethylene nonylphenyl ether (n-10), which is a typical nonionic surfactant, had a large number of repellents. Further, when the sample to which the compound according to the present invention was added was developed with the above-mentioned commercially available developer, no adverse effects were observed on photographic properties (sensitivity, gamma, fog, etc.).

Example 4 Anhydro-9-ethyl-
Add 5,5'-diphenyl-3,3-(disulfoprobyl)oxacarbocyanine hydroxylate, then add a solution of 1 and dibutyl phthalate in ethyl acetate as a macenta coupler, and then add citric acid. to adjust the pH, and add Exemplified Compound 1 to this emulsion.
A silver halide emulsion for use in a green-sensitive layer of a color negative film was prepared by adding Q.2 gs of 1 per kg of emulsion and a hardening agent (2,4-dichloro-6-hydroxytriazine sodium salt). This emulsion was applied onto a subbed cellulose triacetate support to a thickness of 3.0 μm after drying.
The coating was applied at a speed of 20 m/min so that the coating was applied, and after being cooled and set, it was dried. The coating surface of the obtained emulsion layer was completely smooth, free from repelling and unevenness, and the results were satisfactory. This was exposed to green light through a neutral gray wedge. Then, it was developed at 38°C for 3 minutes using a color developer with the following composition.
A good magenta color image was obtained by bleach-fixing in a conventional manner.

Color development N,N-diethylvara phenylenediamine sulfate 2.0
g Sodium sulfite 2.0 g Sodium carbonate (monohydrate) 50.0 g Hydroxylamine hydrochloride 1.5 g Potassium bromide i, o g Add water to 1000 mft (pH 10,8 ± 0.1
) Example 5 On one side of a polyethylene terephthalate support having subbing layers on both sides, an antihalation layer containing a water-soluble magenta dye, gelatin, and an ethyl acrylate polymer prepared in Formulation 1 below was applied in advance. put. On the other hand 4.
3-carboxymethyl-5- to a ripened high contrast silver halide emulsion containing 5% by weight gelatin, 195 mol% silver bromide, 80 mol% silver chloride and 0.5 mol% silver iodide.
[2-(3-ethylthiazolinidene)ethylidene] rhodanine, 4-hydroxy-1,3,3a, 7-chitrazaindene, mucochloric acid, ethylene oxide group 50
Polyoxyethylene nonylphenyl ether and N-(γ-diethylaminopropyl)-N'-phenylurea containing 100% polyoxyethylene are added in normally used amounts, and then divided into two equal parts, and the first part is further divided into four equal parts. 200 mft of ethyl acrylate polymer dispersions prepared according to the following formulations (1) to (4) were added to each kg of emulsion, and the mixture was thoroughly stirred and mixed. No dispersion is added to the remaining portion. Each portion of the emulsion was coated on the side of the support opposite the antihalation layer in proportions such that 100 m2 contained 55±5 mg of silver.

Prescription (1) 3 kg of ethyl acrylate and 100 g of Exemplified Compound 3 of the present invention and 2 g of Exemplified Compound 21 as dispersants are added to distilled water at 12° C. and emulsified by stirring at 500 to 800 rpm. Next, 15 g of potassium persulfate O as a polymerization initiator is added, and the mixture is heated and maintained at 90 to 100°C while stirring. If the reaction is continued for 6 hours, the polymerization will be completely completed. By carrying out steam distillation for 1 hour to remove some residual particles, the desired stable aqueous dispersion of ethyl acrylate polymer can be obtained. The solid vinyl polymer particles in these dispersions had a particle size of about 0.02 to 0.1 μm, and most of them were spherical particles with a size of about 0.05 μm.

Prescription (2) Preparation was made in the same manner as in Prescription (1) using the anionic surfactant (a) shown below instead of Exemplary Compound 3.

(a) Prescription (3) The following anionic surfactant (b
) according to recipe (1).

Surfactant (b) Prescription (4) In place of Exemplary Compound 3, sodium dodecylbenzenesulfonate (abbreviated as SDS) was used, and the same procedure as Prescription (1) was followed.

On each coated emulsion layer, Exemplary Compound 3, the above surfactants (a), (b) and S
DS to 1 to 10 g gelatin aqueous solution, respectively.
A protective layer was prepared by applying 0 mg of the coating solution to a dry film thickness of 1 μm using the combinations shown in Table 3.

(Left below) Using a tungsten light source on each of these sample films,
1/2 of each sample area was exposed to light through a 150-line macenter contact screen, and the remaining 1/2 was exposed to light in a wedge manner, and then developed using developers I and 11 shown in Table 4. Development processing was carried out at a temperature of 25° C. and a development time of 2 minutes.

After the development process, the photographic sensitivity was measured and the halftone quality was observed using an optical microscope with a magnification of 100, and the results shown in Table 5 were obtained.

(Leaving space below) Table 4 Developer formulation sensitivity Optical density 1.5 + reciprocal of exposure amount for fog (control is set to 100 and expressed as relative sensitivity to it) Stability of latex - K N 03 is 0 in polymer latex 40mjZ Added .29g and 05gm and evaluated the agglomeration state after standing for 3 hours (visual judgment) A: No change
Bz White turbidity C: Coagulum present D Nislurry-like halftone dot quality, 50% halftone dot quality was observed and visually graded into A to D.

A: Excellent B: Acceptable for practical use C: Poor D: Very poor The minimum weight of the metal needle that causes scratches (scratching strength) was determined.

As is clear from Table 5, the photosensitive material containing the compound of the present invention and polymer latex provides almost the same sensitivity in both developers (I) and (I+) having different ionic strengths. That is, the dependence on the developer is small. Polymer latex emulsion polymerized using the compound of the present invention is stable in the presence of an electrolyte, and by adding it, excellent scratch strength can be obtained, and there is almost no change in sensitivity. On the other hand, the comparative sample has poor polymer latex stability and poor halftone dot quality after lithographic development. It also has low scratch strength.

[Effects of the Invention] The silver halide photographic material of the present invention can be coated not only at low speed but also at high speed (70 m
/min), an extremely uniform coating film of a hydrophilic colloid layer is formed. That is, uneven coating and repellency of the coating film do not occur. Moreover, it does not adversely affect photographic characteristics. Furthermore, in the photographic material containing the surfactant and polymer latex of the present invention, coating unevenness and repelling of the coating film do not occur, and there is no adverse effect on the photographic quality, especially the physical properties of the coating film, such as photosensitive materials for printing. without degrading the quality of the halftone dots.

When the surfactant of the present invention is used in color photographic emulsions, it not only does not cause uneven coating or repelling of the coating film, but also provides exceptional effects that have not been seen before, such as very clear and high-quality color images. It is something to play.

Applicant for the above patents: Roku Konishi Photo Industry Co., Ltd. Representative Patent Attorney Miki Nakajima Written amendment for one person's procedure (own ship December 1985, Commissioner of the Japan Patent Office Black 1) Akio Tono 1, Indication of the case 1988 Patent Application No. 212679 2, Title of the invention Silver halide photographic light-sensitive material containing a novel surfactant 3, Relationship with the amended person's case Name of patent applicant (127) Roku Konishi Photo Industry Co., Ltd. Representative Ide Keio 4, agent address 11-15, Ichibancho, Chiyoda-ku, Tokyo 102
Date of amendment order Motu 6, Subject of amendment Column 7 of Detailed Description of the Invention, Contents of amendment Attachment 1 2≦'ii'n, 7 Contents of amendment 1) " Correct "parent wood colloid" to "hydrophilic colloid".

2) In the specification, page 14, line 5, "bisexual type" is corrected to "bisexual type."

Procedural Amendment (Spontaneous) Date: 77th May, 1985 1. Indication of the Case: Patent Application No. 212679 of 1988 2. Name of the Invention: Silver halide photographic light-sensitive material containing a novel surfactant 3. Person making the amendment Relationship to the case Patent applicant name (127) Konishiroku Photo Industry Co., Ltd. Representative Keio Ide 4 Address of agent 11-15 Ichibancho, Chiyoda-ku, Tokyo 102
Date of amendment order Voluntary 6, Subject of amendment Section 7 of Detailed Description of the Invention, Contents of amendment 1) Compound 9 on page 10 of the specification "C5H10 Cg, H+aCONIl:)I2CI(2GOOK" is corrected to "" .

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layer or the hydrophilic colloid layer containing polymer latex has a carbon number of 4 or more. having a saturated or unsaturated hydrocarbon chain with branches of or/and having the general formula [I
] A silver halide photographic material containing a surfactant having a partial structure represented by: General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ R_1 and R_2 represent a saturated or unsaturated hydrocarbon group having 4 to 25 carbon atoms, and A represents a trivalent linking group.