JPH0746211B2 - Silver halide photographic light-sensitive material containing novel surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a silver halide photographic light-sensitive material containing a novel surfactant, and more specifically, it is free from cissing and unevenness. The present invention relates to a silver halide photographic light-sensitive material containing a novel surfactant which has excellent film properties, can be applied uniformly, is a good dispersant for additives, and does not adversely affect photographic properties.

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 photographic support. These photographic constituent layers have various functions such as an undercoat layer, an intermediate layer, a photosensitive layer, a surface protective layer, etc. Therefore, in producing a photographic light-sensitive material, gelatin or the like is often used on a support. There are cases where a plurality of different photographic constituent layers containing the hydrocolloid of are simultaneously coated in layers, and at this time, the coating liquid is a coating layer that is uniform and high speed without causing coating failure such as cissing, A thin coating is required. In order to satisfy this requirement, it has been attempted to add a surfactant to the coating liquid, and many compounds are known as such a surfactant. 59-50
969, Japanese Patent Laid-Open No. 51-3219, Belgian Patents 708347, 723690, etc. In addition, a hydrophilic colloid liquid containing a hydrophobic synthetic polymer such as an acrylic ester as a dispersion is applied to an organic solvent of a hydrophobic photographic additive such as a coupler, an ultraviolet absorber and an optical brightener, or a hydrophilic binder. Also in this case, a surfactant is indispensable as a dispersant.

However, the surfactants used in photographic light-sensitive materials have good development processability (that is, wettability on the film surface) that requires photographic characteristics such as photographic sensitivity, fog and gradation and rapid processability such as the speed of development. Is good and there is no adhesion of bubbles, etc.) and it is necessary not to adversely affect the physical properties of the film. Conventionally, generally, a surfactant such as an anionic or nonionic surfactant is It is not preferable in terms of wetting, and in the latter case, repelling is often generated. Therefore, when these surfactants are added to the photographic coating solution as a coating aid, uniform coating of the photographic coating solution cannot be obtained. In addition, it is not preferable because uneven development occurs during development.

Furthermore, it has been difficult to say that the conventionally used surfactants are always sufficiently satisfactory in film physical properties.

Therefore, as a result of various studies on the above-mentioned problems and drawbacks, the present inventors have used a novel surfactant having a certain kind of substituent introduced therein, particularly for anionic surfactants. It has been found that the above problems can be solved without adversely affecting the photographic characteristics. Therefore, the present invention is based on the findings,
It has been completed.

OBJECTS OF THE INVENTION Accordingly, a first object of the present invention comprises a dispersion of lipophilic photographic additives which does not substantially adversely affect photographic properties such as photographic speed, fog, gradation, speed of development. It is to provide a silver halide light-sensitive material.

A second object of the present invention is to provide a silver halide light-sensitive material excellent in film physical properties in which a hydrophilic colloid layer made of a hydrophilic colloid such as a binder is uniformly applied on a support.

A third object of the present invention is to obtain a stable photographic processing property which has good wettability with respect to a photographic processing solution, does not generate bubbles even when automatically performing development processing at a high speed, and has no unevenness. Another object of the present invention is to provide a silver halide photographic light-sensitive material.

The object of the present invention Configuration of the Invention] is at least one -OR _2, -OCOR ₂
It was achieved by using a surfactant having a substituent of More specifically, the present invention is a silver halide photographic light-sensitive material characterized in that at least one hydrophilic colloid layer on a support contains a surfactant represented by the general formula [I]. is there.

General formula [I] [In the formula, R ₁ represents an alkyl group or an alkenyl group having 3 to 25 carbon atoms, X represents -OR ₂ or -OCOR ₂ , Y represents a group having a hydrophilic group, and R ₂ represents 1 carbon atom. ~ 25 alkyl group, alkylaryl group, alkenyl group or alkenylaryl group. In the general formula [I], the hydrophilic group for Y is
Anionic group such as —COOM, —SO ₃ M, —OPO (OM) ₂ (wherein M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkylammonium, etc.).

A group (wherein R ₃ , R ₄ , and R ₅ are alkyl groups having 1 to 12 carbon atoms,
An alkenyl group and a phenyl group are preferable, and X is O
H, Cl, Br, I, NO 3, CH 3 COO, CH 3 -SO 3, -SO 3, CH 3 SO 3, (SO 4) 1/2, polycarboxylic acid, and the like).

And amphoteric groups (l is 1 to 6) or nonionic groups such as polyoxyethylene group, polyoxypropylene group and 2-methoxy-oxypropylene group.

Among the hydrophilic groups in Y, the anionic group is most preferable, and in the case of the nonionic group, it is preferable to use it in combination with the anionic surfactant.

The details are shown below.

The surfactant of the present invention is 0.01 to 5 per 1 kg of various photographic coating solutions.
It may be added in the range of 0 g, but usually 0.05 to 5 g is suitable. As a method of addition, it is preferable to add it as a solution in water or a solvent that can be mixed with methanol or other water.

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

In the silver halide photographic light-sensitive material of the present invention, by adding the surfactant of the present invention, an extremely uniform coating film of a hydrophilic colloid layer is formed not only in low-speed coating but also in high-speed coating (50 m / min or more). . That is, uneven coating and cissing of the coating film do not occur.

Further, it does not affect the photographic characteristics, and does not deteriorate the halftone dot quality in a photosensitive material for printing, for example.

The surfactant of the present invention is useful as a dispersant when a photographic light-sensitive material contains a coupler, a hydroquinone such as an alkylhydroquinone, an ultraviolet absorber, a lipophilic substance (or a hydrophobic substance) such as a sensitizing dye. is there.

The lipophilic substance is finely and stably dispersed in a hydrophilic colloid aqueous solution in the presence of the surfactant of the present invention to obtain a solution obtained by dissolving it in a water-insoluble organic solvent having a high boiling point, and use it as a direct coating liquid. , It can be further added to a coating solution such as a photographic emulsion.

Even when a large amount of the surfactant of the present invention was added to a photographic emulsion, no adverse effects on photographic characteristics were observed.
Further, the surfactant of the present invention can be used in combination with other anion, cation, nonion and amphoteric type surfactants.

In this case, these surfactants may be added to the same layer or different layers among the plurality of hydrophilic colloid layers. As other surfactants that can be used in combination, for example, Ryohei Oda and Kazuhiro Teramura [Synthesis of surfactants and their applications] (Maki Shoten
1964 edition).

In the silver halide photographic light-sensitive material of the present invention, the surfactant of the present invention is allowed to exist together with the polymer latex in the hydrophilic colloid. 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. Of these polymerization methods, the emulsion polymerization method is preferable.

In this emulsion polymerization method, the reaction temperature is 20 to 180 ° C., more preferably 40 to 100 ° C., water, a hydrophobic vinyl monomer of 10 to 50 wt% relative to water, and 0.
It can be carried out using 05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of an 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 according to the purpose.

When the surfactant of the present invention is present at the time of polymerization, the surfactant of the present invention can be used in a part or all of the amount added to the photographic coating liquid.

In polymerizing the polymer latex used in the present invention, it is possible to use other anionic, cationic, amphoteric or nonionic surfactant in combination with the surfactant of the present invention, or an emulsifier such as a water-soluble polymer. it can.

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

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

The monomer used to obtain the polymer latex is not particularly limited as long as it is a polymerizable ethylenic monomer, but is preferably a hydrophobic vinyl monomer. As such a hydrophobic vinyl monomer, acrylic acid ester, methacrylic acid ester, vinyl acetate, styrene, vinyl chloride, vinylidene chloride, butadiene and the like are particularly preferably used.

The polymer latex used in the present invention is preferably 80% by weight or less based on the hydrophilic colloid, more preferably 5% by weight.
% To 50% by weight, and the coating amount is preferably about 0.01 to 5.0 g per 1 m ^{2 of the} hydrophilic colloid layer, and more preferably
It is 0.1 to 1.0 g.

The surfactant of the present invention is used by adding it to various hydrophilic colloid coating compositions generally used in the photographic field.

As the hydrophilic colloid forming the hydrophilic colloid layer of the photographic light-sensitive material of the present invention, in addition to the most representative gelatin, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, synthetic polymers such as polyacrylamide, etc., alone or in a mixture. Can be mentioned. A water-insoluble polymer such as polyalkyl acrylate or polyalkyl methacrylate may be further dispersed in the hydrophilic colloid.

The silver halide photographic light-sensitive material of the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Silver is used.

In addition to silver halide photographic emulsions, direct positive photographic emulsions with silver halide grains whose surfaces have been fogged beforehand by light, reducing substances, precious metal salts, etc., or internal latent image type which gives a positive image by surface phenomenon. A photographic emulsion can also be used.

The silver halide emulsion may be chemically sensitized with a sulfur compound, a selenium compound, a noble metal compound or the like, or spectrally sensitized with a sensitizing dye by a conventional method.

The coating solution used to form the photographic constituent layer including the hydrophilic colloid layer according to the present invention is an inorganic hardener such as chromium alum, chromium acetate, etc., formaldehyde, mucochloric acid, an active halogen compound, an active vinyl compound, Various photographic hardeners such as organic hardeners such as ethylene imide compounds may be included. The photographic light-sensitive material of the present invention may contain various emulsion stabilizers such as azaindene compounds, phenylmercaptotetrazole and the like, antifoggants and the like. In addition, various additives necessary for obtaining a photographic light-sensitive material such as silicone, fluorine-containing compounds, surface-modified detergents such as fatty acid esters, various color couplers in color light-sensitive materials, filter dyes, and irradiation. Dyes such as prevention dyes, plasticizers and the like may be contained.

The silver halide photographic light-sensitive material according to the present invention includes a normal black-and-white silver halide photographic light-sensitive material (for example, X-ray black-and-white light-sensitive material, printing black-and-white light-sensitive material, etc.) Color reversal film, color negative film, color positive film, etc.) and various photographic light-sensitive materials.

The supports of these photographic light-sensitive materials include fibrin ester,
A plastic film such as polycarbonate or polyethylene terephthalate, paper, glass, or the like is used.

[Examples] The present invention will be described in more detail with reference to the following examples.
This is an example, and the present invention is not limited to this. All percentages are by weight unless otherwise specified.

Example 1 To a silver chlorobromide emulsion (silver chloride 50 mol%) containing 7% gelatin and 5% silver halide, 0.2 kg of Exemplified Compound 1 was added per 1 kg of the emulsion.
g and 150 g of polyethyl acrylate latex having a particle size of 0.05 μm (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 m / min, and set by cooling. A gelatin containing 1 g of each of the exemplified compounds 2, 4, 7, and 8 and 100 g of a polyethyl acrylate latex having a particle size of 0.05 μm (solid content: 20% by weight) in 1 kg of a 2.5% gelatin solution as a protective layer. The solution was applied, cooled and set, and then dried.

The silver halide emulsion layer of the prepared film and the hydrophilic colloid layer of the protective layer were free from bubbles and cissing and could be uniformly coated at a coating speed of 50 m / min. Further, when these samples were developed with a usual methol hydroquinone developer, no bubbles were generated during the development, an even image was obtained, and no adverse effects were observed on photographic characteristics (sensitivity, gamma, fog). It was

Example 2 A high-sensitivity high-contrast emulsion containing 6% gelatin and 6% silver iodobromide (1.5 mol% silver iodide) was prepared. This photographic emulsion contains 0.01 g of sodium dodecylbenzenesulfonate and the exemplified compound 16
Was added as a 2% aqueous solution so as to be contained in the range of 0.01 to 2.5 g per 1 kg of emulsion to prepare samples with different addition amounts.

This emulsion was coated on a cellulose triacetate support having an undercoat layer and dried. As shown in Table 1, the addition of Exemplified Compound 16 significantly reduces the number of cissing.

Even if it is a high-sensitivity high-contrast emulsion, does it cause fog?
Alternatively, it was possible to obtain a light-sensitive material having very few good photographic characteristics.

Example 3 0.15 g of saponin and polyoxyethylene nonylphenyl ether (chain length of polyoxyethylene: 15) per 1 kg of a negative photographic emulsion containing 7% gelatin and 8% silver iodobromide (7 mol% silver iodide). Photographic emulsion containing 0.06g and 7% gelatin aqueous solution
The compound 1, 8, 1 according to the present invention is as follows per 1 kg:
9, 23 or for comparison, a surface protective layer to which a known surfactant is added, respectively, is applied in a multi-layer coating method so that the dry film thickness becomes 5 μm and 1 μm, respectively, on the undercoated triacetyl cellulose support. Simultaneous coating, cooling setting, and drying. The surface protective layer of each of the obtained photographic film samples was inspected, and the number of points (repellency) where the coating became nonuniform was counted. In addition, a commercially available Sakura SD-20 (Konishi Rokusha Kogyo Co., Ltd.) metol-hydroquinone developer was dropped onto each of the samples placed horizontally, and a contact angle measuring device (Goniometer G-1 type manufactured by Elma Co.)
The contact angle was measured by. If the value of this contact angle is large, the film is hard to wet when a photographic film is put in the developing solution, which causes bubbles to adhere and uneven development.
Therefore, it is desirable that the contact angle is small. Second
The table shows these results.

As is clear from Table 2, when the present invention is carried out, the contact angle is small and cratering is hardly seen. On the other hand, in the case of sodium lauryl sulfate and sodium dodecylbenzene sulfonate, which are typical anionic surfactants, the cissing number decreases but the contact angle is large, and the film surface has water,
The developer was liable to repell, and uneven development occurred. In addition, the number of cissing was large with polyoxyethylene nonylphenyl ether (n = 10), which is a typical nonionic surfactant.
Further, when a sample containing the compound according to the present invention was developed with the above-mentioned commercially available developer, no adverse effects on the photographic characteristics (sensitivity, gamma, fog, etc.) were observed.

Example 4 In a high-sensitivity negative type silver iodobromide (4.0 mol% silver iodide) emulsion, anhydro-9-ethyl-5,
5'-Diphenyl-3,3- (disulfopropyl) oxacarbocyanine hydroxide was added, then as a magenta coupler, After adding a solution of dibutyl phthalate in ethyl acetate and citric acid to adjust the pH, 0.2 g of Exemplified Compound 5 was added to 1 g of the emulsion to disperse the emulsion, and a hardener (2,4-dichloro- 6-hydroxytriazine sodium salt) was added to prepare a silver halide emulsion used in the green-sensitive layer of a color negative film. This emulsion was coated on a subbed cellulose triacetate support at 20 m / m so that the thickness after drying would be 3.0μ.
It was applied at a speed of a minute, cooled and set, and then dried. The coated surface of the obtained emulsion layer was completely smooth, and there was no cissing or unevenness, which was a satisfactory result. It was exposed to green light through a neutral gray light wedge. Then, using a color developer having the following composition, development was carried out at 20 ° C. for 10 minutes, and bleach-fixing was carried out by an ordinary method to obtain a good magenta color image.

Color developer N, N-diethylparaphenylenediamine sulfate 2.0g Sodium sulfite 2.0g Sodium carbonate (monohydrate) 50.0g Hydroxylamine hydrochloride 1.5g Potassium bromide 1.0g Add water to 1000ml (pH 10.8 ± 0.1) Example 5 An antihalation layer containing a water-soluble magenta dye, gelatin and an ethyl acrylate polymer prepared according to the following formulation-1 was coated on one side of a polyethylene terephthalate support having subbing layers on both sides. deep. Meanwhile 4.5
To an aged hard tone silver halide emulsion containing wt% gelatin, 19.5 mol% silver bromide, 80 mol% silver chloride and 0.5 mol% silver iodide was added 3-carboxymethyl-5- [2-
(3-Ethyl-thiazolinidene) ethylidene] rhodamine, 4-vidroxy-1,3,3a, 7-tetrazaindene, mucochloric acid, polyoxyethylene nonylphenyl ether containing 50 ethylene oxide groups and N- (γ-diethylamino) Propyl) -N'-phenylurea was added in a commonly used amount and then divided into two equal parts, the first part was further divided into four equal parts, and ethyl acrylates prepared by the following formulations (1) to (4), respectively. Polymer dispersion, emulsion 1K
200 ml was added to g and well mixed with stirring. No dispersion is added to the rest. The emulsion of each part was coated on the side of the support opposite to the antihalation layer in such a proportion that 100 m ² 55 ± 5 mg of silver was contained.

Formulation (1) To 12 liters of distilled water, 3 kg of ethyl acrylate and 100 g of Exemplified compound 19 of the present invention as a dispersant are added and stirred at 500 to 800 rpm to emulsify. Next, 0.15 g of potassium persulfate as a polymerization initiator is added, and the mixture is heated with stirring and kept at 90 to 100 ° C. Reaction 6
If the time is continued, the polymerization is completed. The desired stable ethyl acrylate polymer aqueous dispersion can be obtained by steam distillation for 1 hour to remove some residual monomers.
The particle size of the solid vinyl polymer in these dispersions was about 0.02 to 0.1 μm, and most of them were spherical particles having a uniform size of about 0.05 μm.

Formulation (2) Anionic surfactant (a) shown below was used instead of Exemplified Compound 19 in Formulation (1), and the same preparation was performed.

Formulation (3) According to Formulation (1), the following anionic surfactant (b) was used in place of Exemplified Compound 19.

Surfactant (b) Formulation (4) According to Formulation (1), sodium dodecylbenzenesulfonate (abbreviated as SDS) was used in place of Exemplified Compound 19.

On each of the coated emulsion layers, a 6% aqueous gelatin solution was further added with Exemplified Compound 19, the above surfactants (a), (b), and SD.
100 mg of S was added to each 1 Kg gelatin aqueous solution, and the combination of coating solutions as shown in Table 3 gave a dry film thickness of 1
It was applied so as to have a thickness of μ to form a protective layer.

For each of these sample films, using a tungsten light source,
Pass the 150-line magenta contact screen to 1/2 of each sample piece area, and do not pass the screen to the remaining 1/2,
After light-wedge exposure, it was developed using the developing solutions I and II shown in Table 4 at a developing temperature of 25 ° C. and a developing time of 2 minutes.

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

Sensitivity: Optical density 1.5 + reciprocal of fog exposure (displayed as relative sensitivity with control as 100) Latex stability: 0.29 g and 0.5 g of KNO ₃ was added to 40 ml of polymer latex and left for 3 hours A: No change B: White turbidity C: Coagulated substance present D: Slurry halftone dot quality: 50% halftone dots were observed and qualitatively classified into A to D.

A: Excellent B: Practically acceptable C: Inferior D: Very inferior [Scratch strength] After developing, fixing and washing in the above-mentioned treatment process, the membrane surface is pulled with a heavy metal needle while immersed in washing water. The weight of the lowest scratched metal needle (scratch strength) was determined.

As is clear from Table 5, the light-sensitive material containing the surfactant of the present invention and the polymer latex gives almost the same sensitivity in both the developers (I) and (II) having different ionic strengths. That is, the dependency on the developing solution is small. The polymer latex emulsion-polymerized using the surfactant of the present invention is stable in the presence of an electrolyte, and by adding it, excellent scratching strength 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 and inferior in the halftone dot quality of the lith development. Also, the scratch strength is small.

[Effect of the Invention] The silver halide photographic light-sensitive material of the present invention is a coating film of a hydrophilic colloid layer which is extremely uniform not only in low-speed coating but also in high-speed coating (50 m / min or more) by adding a novel surfactant. Is formed. That is, uneven coating and cissing of the coating film do not occur. In addition, it does not adversely affect the photographic characteristics. Further, even in a photographic light-sensitive material containing a surfactant and a polymer latex of the present invention, coating unevenness and cissing of the coating film do not occur and the photographic quality, particularly the physical properties of the coating film, are not adversely affected.
For example, it does not deteriorate the halftone dot quality of the photosensitive material for printing.

Even when the surfactant of the present invention is used in a color photographic emulsion, not only uneven coating and cissing of the coating film do not occur, but
A very clear, good quality color image is obtained. Further, it has good wettability with respect to the photographic processing liquid, and bubbles are not generated even when the development processing is performed automatically at a high speed, and stable photographic processing characteristics without unevenness can be obtained, which is unprecedented. It has a special effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-48-30933 (JP, A) JP-A-51-7917 (JP, A) JP-A-53-129623 (JP, A) JP-A-54- 98235 (JP, A) JP 55-22754 (JP, A) JP 55-56867 (JP, A) JP 56-104329 (JP, A) JP 57-104927 (JP, A) JP-A-58-153925 (JP, A) JP-A-60-76741 (JP, A) JP-A-60-209732 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material characterized in that at least one hydrophilic colloid layer on a support contains a surfactant represented by the general formula [I]. General formula [I] [In the formula, R ₁ represents an alkyl group or an alkenyl group having 3 to 25 carbon atoms, X represents -OR ₂ or -OCOR ₂ , Y represents a group having a hydrophilic group, and R ₂ represents 1 carbon atom. ~ 25 alkyl group, alkylaryl group, alkenyl group or alkenylaryl group. ]