JP2613384B2 - Silver halide photographic materials containing new surfactants - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material containing a novel surfactant.

[Background of the Invention]

Generally, a photographic light-sensitive material is provided with a plurality of photographic constituent layers containing a hydrophilic colloid on a 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, in producing a photographic photosensitive material, a hydrophilic material such as gelatin is often provided on a support. In some cases, a plurality of different photographic constituent layers containing sexual colloids are simultaneously coated in layers, and in this case, the coating solution is applied uniformly and in a high bundle without causing a coating failure such as cissing. Required to apply. To satisfy this request,
Conventionally, a surfactant has been added to the coating solution.Examples of the surfactant include JP-B-45-5331, JP-B-59-50969, JP-A-51-3219, Belgian patents 708347, and 72369.
The description is recognized in the specification of No. 0 and the like. The surfactant is used not only as a coating aid but also as an organic solvent for a hydrophobic photographic additive such as a coupler, an ultraviolet absorber, a fluorescent brightener, or a hydrophobic synthetic polymer such as an acrylate ester. It is also used as a dispersant when applying a hydrophilic colloid liquid containing a polymer latex as a dispersion.

However, surfactants used in photographic light-sensitive materials require photographic properties such as photographic sensitivity, fog, and gradation, and development processing properties that require rapid processing properties such as the speed of development (ie, good wetting on the film surface). And no adhesion of bubbles), but many of the surfactants that have been used in the past have been used as coating aids such as hydrophilic colloid liquids in terms of wetting. It is not preferable, and as a dispersant for a photographic additive, it is not preferable because it has a high viscosity and generates many bubbles and cissing. In particular, when a polymer latex is added to a hydrophilic colloid layer to improve the film properties, for example, it is described in U.S. Patent No. 2,852,386, JP-B-57-9051, and JP-A-57-200031. It is necessary to consider the scratch strength, dimensional stability, flexibility, etc. of the hydrophilic colloid layer as in this case, and in this case, the polymer latex is likely to agglomerate in gelatin, which may affect the dispersion stability and, consequently, the coatability. It was always a concern and not satisfactory. Accordingly, when a surfactant is added to a photographic coating solution, uniform application of the photographic coating solution cannot be obtained, and uneven development occurs during development.

[Object of the invention]

The present invention has been made to solve the above problems,
It has excellent coatability of the hydrophilic colloid to the support, and in this case, even if the colloid contains a polymer latex, it can be uniformly dispersed without aggregation to improve the physical properties of the film, and sensitivity, fog, etc. An object of the present invention is to provide a silver halide photographic light-sensitive material having excellent photographic characteristics. In particular, it is an object of the present invention to provide a silver halide photographic light-sensitive material having good halftone dot quality in a printing light-sensitive material.

[Structure and operation of the invention]

The present invention relates to a silver halide photographic material having at least one hydrophilic colloid layer on a support (except for a silver halide photographic material which is a photothermographic material). The silver halide is characterized in that the first layer contains a surfactant represented by the following general formula [I] having a polyoxazoline chain and a hydrocarbon group having 4 or more carbon atoms at the end of the polyoxazoline chain. This is a photographic light-sensitive material, and the above object was achieved by this configuration.

In the present invention, at least one of the hydrophilic colloid layers contains a surfactant having a polyoxazoline chain and a hydrocarbon group having 4 or more carbon atoms at the end of the polyoxazoline chain. The polyoxazoline chain is a binding chain obtained by ring-opening polymerization of oxazoline.

The surfactant contained in the silver halide photographic light-sensitive material of the present invention is particularly one represented by the following general formula [I].

General formula [I] In the formula, R, R ′, R ″ are groups having an alkyl group, an alkenyl group or an aryl group having 1 to 22 carbon atoms,
Any of R ′ and R ″ is an alkyl group having 4 or more carbon atoms,
A group having an alkenyl group or an aryl group, among these substituents, those substituted with fluorine are also included in the present invention.

 N represents an integer of any of 1 to 50.

In practicing the present invention, of the above general formula [I], those represented by the following general formulas [II] and [III] are more preferable.

General formula (II) General formula (III) In the above general formulas (I) and (II), R ₁ , R ₄ and R ₇
Represents a substituent of any of an alkyl group, an alkenyl group and an aryl group having 1 to 22 carbon atoms, and R ₂ , R ₃ , R ₅ and R ₆ represent the above substituents and a hydrogen atom. However,
R ₂ and R ₃ are not simultaneously hydrogen atoms.

Further, the hydrogen atom bonded to the carbon atom of each substituent represented by R ₁ to R ₇ also includes those substituted with a fluorine atom.

Examples of the surfactant represented by the above general formula are shown below, but the present invention is not limited to the following compounds.

Examples of the surfactant according to the present invention include “Ring-opening polymerization (I), (II)” written by Takeo Saegusa (Kagaku Doujin, 1971) and “Block and Graft Polymerization (Bl
ock and Graft Polymerization) by RJ Selesa (Jalm
It can be easily synthesized by the method described in Wily & Soms (1973).

The surfactant of the present invention is 0.00.0 kg / kg of various photographic coating solutions.
Although it can be added in the range of 1 to 50 g, usually 0.05 to 5 g is preferable. As an addition method, it is preferable to add the compound by dissolving it in water or methanol or another hydrophilic solvent.

The surfactant of the present invention can be used as a coating aid in a coating liquid for any hydrophilic colloid layer such as an undercoat layer, an intermediate layer, a photosensitive layer, and a surface protective layer, which are photographic constituent layers constituting a silver halide photographic material. The hydrophilic colloid layer may be a photosensitive layer or a non-photosensitive layer.

The surfactant of the present invention is a coupler in a photographic light-sensitive material,
It is suitable as a dispersant when lipophilic substances such as alkyl hydroquinones, ultraviolet absorbers and sensitizing dyes are contained.

The lipophilic substance is used as a coating solution by directly dispersing a solution dissolved in a high boiling point hardly water-soluble organic solvent in a hydrophilic colloid aqueous solution in the presence of the surfactant of the present invention, or using the above solution directly. Further, it can be used by adding it to a coating solution such as a photographic emulsion.

The surfactant of the present invention, even when added in a large amount to a photographic emulsion, does not have a risk of inhibiting photographic properties, and is used in combination with other anions, cations, nonions, and amphoteric surfactants. You can also.

In this case, the surfactant can be arbitrarily added to the same or different layers of the plurality of hydrophilic colloid layers. Other surfactants that can be used in combination include
For example, there are those described in Ryohei Oda and Kazuhiro Teramura [Synthesis and Application of Surfactants] (Maki Shoten 1964 Edition).

The surfactant of the present invention can be preferably used in a hydrophilic colloid containing a polymer latex. The polymer latex can be easily produced by redispersing a polymer obtained by an emulsion polymerization method, a solution polymerization method or a bulk polymerization method, and among these polymerization methods, the emulsion polymerization method is preferable.

This emulsion polymerization method comprises a reaction temperature of 20 to 180 ° C., more preferably 40 to 100 ° C., water, 10 to 50% by weight of a hydrophobic vinyl monomer based on water, and 0.05 to 5% by weight of the monomer.
It can be carried out by using a polymerization initiator of 0.1% by weight and an emulsifier of 0.1 to 20% by weight.

During the emulsion polymerization, 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 according to the purpose. can do.

The surfactant of the present invention to be present at the time of polymerization can be used by adding all of the amount added to the photographic coating solution.

The emulsifier is preferably used in view of the stability of the obtained polymer latex over time, the compatibility with the hydrophilic colloid, and the like.

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

As the polymerization initiator used in the polymerization of the polymer latex, for example, potassium persulfate, ammonium persulfate,
Persulfates such as sodium persulfate, 4,4'-azobis-
Sodium 4-cyanovalerate, 2,2'-azobis (2-
Water-soluble azo compounds such as amidinopropane) hydrochloride and hydrogen peroxide can be used.

The molecular weight of the polymer latex when carrying out the present invention is preferably 2,000 to 1,000,000, more preferably 5,
000 to 500,000, and the particle size is preferably 0.01 to 1 μm,
More preferably, it is 0.01 to 0.5 μm.

The monomer used for obtaining the polymer latex is not particularly limited as long as it is a polymerizable ethylenic monomer, but a hydrophobic vinyl monomer is preferable. As the hydrophobic vinyl monomer, acrylates, methacrylates, vinyl acetate, styrene, vinyl chloride, vinylidene chloride, butadiene and the like are particularly preferable.

Content of the polymer latex used in the practice of the present invention is preferably 80 wt% or less with respect to the hydrophilic colloid, and more is preferably 5 wt% or more, the coating amount of the hydrophilic colloid layer 1 m ² per 0.01 5.0 g is preferred, and more preferably 0.1 to 1.0 g.

As the hydrophilic colloid for forming the hydrophilic colloid layer in the present invention, cellulose derivatives, synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide can be used alone or as a mixture in addition to gelatin. A water-insoluble polymer such as polyalkyl acrylate or polyalkyl methacrylate may be further dispersed in the hydrophilic colloid.

Silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide and the like can be arbitrarily selected and used as silver halide used in the present invention. .

Other examples of the silver halide photographic emulsion include a direct positive photographic emulsion having silver halide grains whose surface has been previously fogged with light, a reducing substance, a noble metal salt, or the like, or an internal latent image which gives a positive image by surface development. A photographic emulsion can be used.

As the silver halide emulsion, those which have been chemically sensitized with a sulfur compound, a selenium compound, a base metal compound or the like, or spectrally sensitized with a sensitizing dye are preferably used.

When carrying out the present invention, a coating solution for forming a photographic constituent layer is an inorganic hardening agent such as chrome alum, chromium acetate, etc.
Organic film hardeners such as formaldehyde, mucochloric acid, active halogen compounds, active vinyl compounds, ethylene imide compounds and the like can improve coating film properties.

In carrying out the present invention, an azaindene compound,
Various emulsion stabilizers such as phenylmercaptotetrazole, etc., which can contain antifoggants and the like, and other various additives required for obtaining photographic light-sensitive materials, such as silicone, fluorine-containing compounds, fatty acid esters, etc. Modified detergents, dyes such as various color couplers, filter dyes and anti-irradiation dyes in color photographic materials, plasticizers and the like, and improved photographic properties are used.

The silver halide photographic light-sensitive material according to the present invention is a black-and-white silver halide photographic light-sensitive material (for example, a black-and-white light-sensitive material for X-ray,
The present invention can be applied to various photographic light-sensitive materials such as a black-and-white light-sensitive material for printing, and a multilayer color photographic light-sensitive material (for example, a color reversal film, a color negative film, and a color positive film).

As the support of the present invention, any material can be used as long as it can support the photographic component layer, and examples thereof include a urethane film such as cellulose ester, polycarbonate and polyethylene terephthalate, paper and glass.

〔Example〕

Hereinafter, the present invention will be described based on the following examples, but the present invention is not limited to the following examples. In addition,% display shows weight% unless there is particular notice.

Example 1 A high-sensitivity high-contrast emulsion containing 6% of gelatin and 6% of silver iodobromide (1.5 mol% of silver iodide) was prepared, and 0.01 g of sodium dodecylbenzenesulfonate was added to this photographic emulsion. 8) was added as a 2% aqueous solution, varying in the range of 0.01 to 2.5 g per kg of emulsion, and samples having different addition amounts were prepared as shown in Table 1 below. Latex 150g (solid content 20% by weight)
Was added. Each of these emulsions was coated on a cellulose triacetate support having an undercoat layer and dried. As shown in Table 1, it can be seen that the addition of the exemplified compound (8) greatly reduces the number of repelling. Also, from Table 1, it can be seen that even when the polymer latex is contained, the repelling number is greatly reduced with an increase in the amount of the exemplary compound (6) added. Further, even in the case of a high-sensitivity high-contrast emulsion, no fog was generated or the fog was extremely small, and good photographic characteristics could be obtained.

Example 2 0.15 g of saponin and polyoxyethylene nonyl phenyl ether (polyoxyethylene chain length: 15) per kg of a negative photographic emulsion containing 7% of gelatin and 8% of silver iodobromide (7 mol% of silver iodide) A photographic emulsion containing 0.06 g and a dispersion were prepared by adding 0.10 g of each of the compounds (4), (6) and (8) shown in Table 2 below to 1 kg of a 7% aqueous gelatin solution.

Then, the photographic emulsion and the dispersion were dried on an undercoated triacetylcellulose support at a dry film thickness of 5 μm each.
Sample Nos. 19 to 25 were prepared by simultaneously coating by a multi-layer coating method so as to obtain 1 μm, cooling and setting, and then dried. The surface protective layer of the obtained sample was inspected, and the number of cissing points of each coating solution was counted. Also, commercially available phenidone-
The hydroquinone developer was added dropwise, and the contact angle was measured with a contact angle measuring device (Goniometer G-1 manufactured by Elma). When the photographic film is immersed in a developing solution as the contact angle increases, the film hardly wets, causing bubbles to adhere and uneven development. Accordingly, the smaller the value of the contact angle, the better the development.

As is clear from Table 2 above, Sample No. 2 according to the present invention
Nos. 0 to 22 have small contact angles and hardly any repelling. In contrast, in Comparative Samples Nos. 24 and 23 to which sodium lauryl sulfate and sodium dodecylbenzenesulfonate as anionic surfactants were added, although the repelling number was reduced, the contact angle of the developer dropped on the film surface was large, It can be seen that the degree of wetting with the developing solution is poor, causing uneven development. Also, it can be seen that Comparative Sample No. 25 to which polyoxyethylene nonyl phenyl ether (n = 10), which is a nonionic surfactant, was added, had a large number of cissing at the time of coating.

Further, when each of the above samples was developed with a commercially available developer, as shown in Table 2, both the sensitivity and the fog were the same as those of Sample Nos. 20 to 22 of the present invention.
Is not inferior to the comparative sample No. 23 to 25 which is a conventional product,
It turns out that it is favorable.

Example 3 On one side of a polyethylene terephthalate support having an undercoat layer on both sides, an antihalation layer containing a water-soluble magenta dye, gelatin and an ethyl acrylate polymer prepared by the following formula (1) is previously coated. . on the other hand,
4.5% by weight gelatin and 19.5 mol% silver bromide, 80 mol%
A ripened high contrast silver halide emulsion containing silver chloride and 0.5 mol% of silver iodide was added with 3-carboxymethyl-5- [2
-(3-ethyl-thiazolinidene) ethylidene] rhodanine, 4-hydroxy-1,3,3a, 7-tetrazaindene,
Mucochloric acid, polyoxyethylene nonylphenyl ether containing 50 ethylene oxide groups and N- (γ-diethylaminopropyl) -N′-phenylurea are each added in usual amounts, and then divided into two equal parts. The emulsion was divided into four equal portions, and 200 ml per 1 kg of the emulsion was added to the dispersion of the ethyl acrylate polymer prepared according to the following formulas (1) to (4), and mixed well with stirring to prepare four types of emulsions. The remaining portion of the equally divided portion was used as it was without adding a dispersion, and the emulsion of each portion was used as an emulsion.On the surface of the support opposite to the antihalation layer, 55 ± 5 mg of silver per 100 cm ² was provided. Each of the above prepared emulsions was coated in the proportions contained.

Formulation (1) To 12 l of distilled water, 3 kg of ethyl acrylate and 10 g of the exemplary compound (8) according to the present invention as a dispersant, 10 g of dextran sulfate and 2 g of propylene glycol were added, followed by 500 to 800 r.
Stir at pm to emulsify. Subsequently, 0.15 g of potassium persulfate as a polymerization initiator was added, and the mixture was heated with stirring and maintained at 90 to 100 ° C., and reacted for 6 hours.

After the reaction, the mixture was subjected to steam distillation for 1 hour to remove a small amount of residual monomers to obtain an intended stable aqueous dispersion of an ethyl acrylate polymer. Incidentally, the size of the solid vinyl polymer particles in these dispersions is distributed in the range of about 0.02-0.1μ,
Almost all were spherical particles of about 0.05 μm.

Formulation (2) A dispersion was similarly prepared using the following nonionic surfactant (a) instead of Exemplified Compound (8) in Formulation (1).

Formulation (3) A dispersion was prepared according to Formulation (1) using the following nonionic surfactant (b) instead of Exemplified Compound (8).

Surfactant (b) C ₉ H ₁₉ COOCH ₂ CH ₂ O ₃ H On each of the coated emulsion layers, the exemplary compound (8), the above surfactants (a) and (b) were further added to a 6% aqueous gelatin solution. Coating solutions obtained by adding 100 mg each to 1 kg of gelatin aqueous solution were applied in a combination shown in Table 3 so that the dry film thickness became 1 μm, and a protective layer was formed to prepare Sample Nos. 26 to 33.

Each of these samples was exposed to a light wedge using a tungsten light source through a 150-line magenta contact screen for half of the area of each sample, and without passing the other half through the screen. Developing treatment was performed at a developing temperature of 25 ° C. and a developing time of 2 minutes using the developing solutions I and II shown in the following.

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

In Table 5 above, the sensitivity, gamma, fog, dot quality, latex stability and scratching strength were determined as follows, and evaluated as follows.

 Sensitivity: same as in Table 1.

Gamma: The light area (logE) required to change the image density from 1.0 to 2.0 was indicated by the reciprocal.

Latex stability: KNO ₃ polymer latex 40
Add 0.29 and 0.5 g to each ml and evaluate the aggregation state after standing for 3 hours (visual judgment) A: No change B: Cloudy C: Coagulated D: Slurry Halftone dot quality: Observe 50% halftone dot And visually classified into A to D.

A: Excellent B: Practically acceptable C: Poor D: Very poor Scratch strength: After developing, fixing and rinsing in the above processing steps, scratch the film surface with a metal needle weighed while immersed in rinsing water Then, the minimum weight (scratch strength) of the metal needle to be scratched was determined.

As is clear from Table 5, photosensitive material samples No. 26 and 29 containing the exemplified compound of the present invention and a polymer latex
Indicates that almost the same sensitivity is obtained in each of the developing solutions I and II having different ionic strengths, and that the dependence on the developing solution is small. Sample No. 26 using a polymer latex emulsion-polymerized using the exemplified compound of the present invention, as shown by the results, is stable in the presence of an electrolyte, and exhibits excellent scratch strength by adding it. Can be obtained, and there is almost no change in sensitivity. On the other hand, the comparative sample is inferior in the stability of the polymer latex, the dot quality of the lith-type development is inferior (see Comparative Sample Nos. 27 and 28), and the scratching strength is also small (Comparative Sample No. 27, 28).

Example 4 Next, layers having the following compositions were sequentially formed on a triacetylcellulose film support to prepare a multilayer color photographic light-sensitive material.

First layer: Antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

Gelatin 2.2 g / m ² Second layer; Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.2 g / m ² Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (emulsion I) composed of AgBrI containing 0.30 μm average particle diameter () 0.30 μm and 6 mol% of AgI Coating amount 1.8 g / m ² Sensitizing dye I 6 × 10 ^-5 mol per mol of silver Sensitizing dye II 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1) 0.06 mol per mole of silver Colored cyan coupler (CC-1) 0.003 mol per 1 mol of silver DIR compound (D-1) 0.0015 mol per 1 mol of silver DIR compound (D- 2) ...... 0.002 mol of gelatin per mol of silver 1.4 g / m ^{2 of} gelatin 4th layer; high sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size () 0.5 μm, AgI 7.0 mol% Monodisperse emulsion composed of AgBrI containing emulsion (Emulsion II): Silver coating amount: 1.3 g / m ² Sensitizing dye I: 3 × 10 ^-5 mol per mol of silver Sensitizing dye II: ^Per mol of silver 1.0 × 10 ^-5 mol Uncoupler (C-1) ... 0.02 mol per mol of silver Colored cyan coupler (CC-1) ... 0.0015 mol per mol of silver DIR compound (D-2) ... per mol of silver 0.001 mol gelatin 1.0 g / m ² 5th layer; intermediate layer (IL) Same as 2nd layer, gelatin layer.

Gelatin 1.0 g / m ² sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I: Silver coating amount 1.5 g / m ² Sensitizing dye III: 2.5 per mol of silver × 10 ⁻⁵ mol Sensitizing dye IV 1.2 × 10 ⁻⁵ mol per mol of silver Magenta coupler (M-1) 0.05 mol per mol of silver Colored magenta coupler (CM-1) 0.009 mol DIR compound (D-1) per mol of silver 0.0010 mol DIR compound (D-3) per mol of silver 0.0030 mol per mol of silver Gelatin 2.0 g / m ² 7th Layer: High-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II: Silver coating amount: 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol sensitizing dye per mol of silver IV: 1.0 × 10 ^-5 mol per mol of silver Magenta coupler (M-1): 0.020 mol per mol of silver Colored magenta coupler (CM-1): 0.002 mol per mol of silver D IR compound (D-3) 0.0010 mol of gelatin per mol of silver 1.8 g / m ^{2 of} gelatin 8th layer; yellow filter layer (YC-1) of yellow colloidal silver and 2,5-di-t-octylhydroquinone A gelatin layer comprising an emulsified dispersion.

Gelatin 1.5 g / m ² Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) consisting of AgBrI containing 0.48 μm in average particle size and 6 mol% of AgI.

Monodisperse emulsion (Emulsion III): Silver coating amount 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): Per mol of silver 0.29 mol gelatin 1.9 g / m ² 10th layer; high-sensitivity blue-sensitive silver halide emulsion layer (BH-1) AgBrI having an average particle size of 0.8 μm and containing 15 mol% of AgI.

Monodisperse emulsion (Emulsion IV): Silver coating amount 0.5 g / m ² Sensitizing dye V: 1.0 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): Per mol of silver 0.08 mol DIR compound (D-2) 0.0015 mol per mol of silver Gelatin 1.6 g / m ² 11th layer; 1st protective layer (Pro-1) Silver iodobromide (AgI 1 mol% average particle size) 0.07 μm) A gelatin layer containing a silver coating amount of 0.5 g / m ² UV absorbers (UV-1) and (UV-2).

Gelatin 1.2 g / m ² 12th layer; 2nd protective layer (Pro-2) Polymethyl methacrylate particles (diameter 1.5 μm) Ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average particle size 2.5 μm) Exemplified compound (14) Gelatin layer containing 3 mg / m ² and formalin scavenger (HS-1) Gelatin 1.2 g / m ^{2 In} addition to the above composition, each layer has a gelatin hardener (H
-1), polyethyl acrylate latex, exemplary compound (3) according to the present invention, and surfactant (SA-1).

Back 1st layer Stearic acid ……… 20mg / m ² Diacetylcellulose ……… 10mg / m ² Back layer 2nd layer Diacetyl cellulose 50 mg / m ² Stearic acid 10 mg / m ² Silica matting agent 50 mg / m ² (average particle size 3μ) However, magenta coupler (M-1) is an exemplary compound (3) and Dispersed by the others And dispersed and applied.

 The compounds contained in each of the above layers are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; anhydro-9-ethyl-3,3 '-Di- (3
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide sensitizing dye III; anhydro-5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl Propyl) oxacarbocyanine hydroxide Sensitizing dye IV; anhydro-9-ethyl-3,3'-di- (3
-Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide sensitizing dye V; anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5' -Methoxythiocyanine In addition, Comparative Sample No. 33 was prepared in the same manner as Sample No. 32 except that sodium dodecylbenzenesulfonate was used in place of the exemplary compound used as the surfactant when preparing Sample No. 32 above. did.

Of the sample Nos. 32 and 33 obtained in this way, the sample No. 32 according to the present invention had good coatability of the emulsion and the like on the support and was formed quite smooth, as shown in the above examples. As shown in Table 6 below, no cissing unevenness was formed. On the other hand, Comparative Sample No. 33 showed the same results as those shown in Table 1 and was poor in applicability.

Next, the samples Nos. 32 and 33 were exposed to wedges with white light, and then subjected to the following developing treatment. The results are shown in Table 6 below.

Processing step (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the processing solution is as follows.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1-2 sulfate 2.0 g anhydrous potassium carbonate 37.3g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

<Bleaching solution> Iron ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to adjust the pH to 1, and adjust the pH to 6.0 using aqueous ammonia.

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 and adjust the pH to 6.0 using acetic acid.

<Stabilizing solution> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konishi Roku Photo Industry Co., Ltd.) 7.5 ml Add water to make 1.

As is clear from Table 6 above, Sample No. 32 of the present invention showed better results in both sensitivity and fog than Comparative Sample No. 33. It turned out to show.

〔The invention's effect〕

As described above, according to the present invention, a hydrophilic colloid containing an emulsion and a polymer latex is excellent in high-speed coating properties (for example, 70 m / min or more), and furthermore, the physical properties of the formed coating film are improved and the photographic properties are improved. A sufficiently secured silver halide photographic material can be provided. In particular, it is possible to provide a silver halide photographic material having a good halftone dot quality in a photographic material for printing.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-230027 (JP, A) JP-A-59-230028 (JP, A) JP-A-60-228535 (JP, A) JP-A 60-228 228536 (JP, A) JP-A-60-229926 (JP, A) JP-A-60-80849 (JP, A) JP-A-62-136642 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one hydrophilic colloid layer on a support (except for a silver halide photographic light-sensitive material which is a heat-developable light-sensitive material). Any one of the layers contains a surfactant represented by the following general formula [I] having a polyoxazoline chain and a hydrocarbon group having 4 or more carbon atoms at the end of the polyoxazoline chain. Silver photographic photosensitive material. General formula [I] In the formula, R, R ′ and R ″ are groups having an alkyl group, an alkenyl group or an aryl group having 1 to 22 carbon atoms;
Any of R "is a group having an alkyl group, alkenyl group or aryl group having 4 or more carbon atoms, and among these substituents, those substituted with fluorine are also included in the present invention. Represents any integer of