JPS63106643A - Silver halide photographic sensitive material having improved physical property as film - Google Patents

Abstract

PURPOSE:To enhance coatability and to improve the physical properties as a film such as scratch strength, dimensional stability and flexbility by incorporating a specified surfactant and polymer latex. CONSTITUTION:When one or more hydrophilic colloidal layers are formed on a support to obtain a photographic sensitive material, a surfactant having a 2-hydroxy-3-sulfopropyl group (salt) and polymer latex are incorporated into at least one of the colloidal layers. The surfactant used is preferably represented by formula I (where R is an org. group having 5-25C alkyl or alkenyl, and M is an inorg. or org. cation). Thus, the physical properties as a film as well as the photographic characteristics and developability are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material with improved film properties and excellent photographic properties and development processability.

[Background of the invention]

In general, hydrophilic colloid films used for producing silver halide photographic materials (hereinafter referred to as photographic materials) are required to have specified strengths not only in terms of photographic properties but also in terms of film physical properties.

Therefore, attempts have been made to improve the physical properties of the hydrophilic colloid layer, such as scratch strength, dimensional stability, and flexibility, by incorporating various polymer latexes into hydrophilic colloids such as gelatin. For example, U.S. Patent 2,852,
No. 386, No. 3,411,911, Special Publication No. 45-53
No. 31, No. 57-9051, JP-A No. 57-20003
The technology is disclosed in No. 1, etc.

When manufacturing such polymer latex, a large amount of surfactant is used as a dispersion stabilizer, but depending on the type and amount of surfactant added, it affects coating properties, photographic sensitivity, fog, gradation, etc. It may have an adverse effect on the photographic properties of the film and the speed of development, such as the speed of development (e.g., good wetting of the film surface and no bubbles adhering to the film surface). Improvement is strongly requested.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide a photographic material that has good coating properties and improved film properties such as scratch strength, dimensional stability, and flexibility.

A second object of the present invention is to provide a photographic material that does not adversely affect photographic properties such as photographic sensitivity, capri, gradation, and speed of development.

A third object of the present invention is to provide a photographic material that has good wettability with a photographic processing solution, and that enables stable photographic processing characteristics without unevenness to be obtained, especially when performing automatic development processing at high speed. The purpose is to provide materials.

A fourth object of the present invention is to provide a photographic material in which a photographic constituent color made of a hydrophilic colloid such as a binder is uniformly coated on a support.

[Structure of the invention]

The above object of the present invention is to provide a photographic light-sensitive material having at least one hydrophilic colloid layer on a support, in which at least one layer of the hydrophilic colloid H has a 2-hydroxy-3-sulfopropyl group (including a salt). This was achieved by including a surfactant and a polymer latex.

The present invention will be explained in more detail below.

The surfactant used in the present invention is preferably one represented by the following general formula.

In the formula, R represents an organic group having an alkyl group or an alkenyl group having 5 to 25 carbon atoms, and M represents an inorganic or organic cation.

R is a lipophilic moiety necessary to exhibit surfactant ability,
There are no special restrictions on its structure. Preferred examples of R include an alkyl group, an alkoxy group, an alkyl- or alkoxy-substituted aryloxy group, an alkylcarbonyloxy group, an alkylsulfonamide group, an acylamido group, and an alkylene oxide residue linked to these groups. If it has an alkenyl group, it has 8 or more carbon atoms.
16 alkenyl groups are preferred.

Preferred examples of M include a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, and an alkylamine having 1 to 3 carbon atoms.

Next, typical examples of surfactants used in the present invention will be shown, but the present invention is not limited thereto.

1, Cs11+tOCHtCIICI! tsO3
Na? 0■ 2, C+ *IIzsOCI[tCIICIIt
SOaNai1 7, C+t11tsC00 (C11tC11tO)
+oCIItCIICIItSOJa14, CJ
, tOcOcllg H 15,C,,111,0(CH,CuI2)! 6C11
ICIICII, SO, ni 16, Cs! L70C
IItCIICIbSO311■ H 17, C+t11t30C11tCIICIItSO-
Nll-0■ These surfactants of the present invention can be easily synthesized by known methods. For example, Exemplary Compound 2 can be obtained by adding sodium l-chloro-2-hydroxypropanesulfonate to a solution of dodecyl alcohol and sodium hydroxide dissolved in diethylene glycol monomethyl ether and then heating the mixture to IOθ°C.

The surfactant of the present invention is 0.00% per IKy of various photographic coating solutions.
The range of 01 to 5Q9 can be added, but usually 0.05 to
5g is appropriate. As for the addition method, it is preferable to add the compound by dissolving it in water, methanol, or other water-miscible solvent. The surfactant of the present invention may be added to the coating solution for any hydrophilic colloid layer constituting the photographic light-sensitive material of the present invention, and if the hydrophilic colloid layer is a photosensitive layer, the non-photosensitive layer It doesn't matter if it is.

The photographic material of the present invention can be coated not only at low speed but also at high speed (501/min or more) by adding the surfactant of the present invention.
Even in this case, an extremely uniform coating film of a hydrophilic colloid layer is formed. In other words, uneven coating and repellency of the coating film do not occur.

Further, it does not affect photographic properties, and does not deteriorate the quality of halftone dots in, for example, photosensitive materials for printing.

In the 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, emulsion polymerization method is preferred.

In this emulsion polymerization method, the reaction temperature is 20 to 180°C.
, more preferably 40 to 10 Q'C, water, 10 to 50% by weight of a hydrophobic vinyl monomer based on the water, 0.05 to 5% by weight of a polymerization initiator based on the monomer, and 0.1
This can be done using ~201i ffi% 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 the present invention can be used in a 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 in place of or in combination with the surfactant of the present invention. Can be done.

Examples of the polymerization initiator used in the emulsion polymerization method for polymer latex of the present invention include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate;
'-Sodium azobis-4-cyanovalerate, 2.2
Water-soluble azo compounds such as '-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 soo, ooo. 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 preferably a hydrophobic vinyl monomer. Examples of such hydrophobic vinyl monomers include acrylic esters, methacrylic esters, vinyl acetate,
Styrene, vinyl chloride, vinylidene chloride, butadiene, etc. are preferably used.

The polymer latex of the present invention is preferably 80% by weight or less, more preferably 5% by weight or less based on the hydrophilic colloid.
50% by weight, and the coating amount is hydrophilic colloid W11.
It is preferably about 0.01 to 5.0 g, more preferably 0.1 to 1.09 g per Il day.

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 polyalkyl 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 fogged with light, reducing substances, noble metal salts, etc., or internal grains that produce positive images through surface development. A latent image type photographic emulsion can also be used.

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

The coating liquid used to form the hydrophilic colloid layer of the present invention includes inorganic hardeners such as chrome alum, chromium chloride, formaldehyde, mucochloric acid, active halogen compounds, active vinyl compounds, ethyleneimide compounds, etc. Various photographic hardeners may be included, such as organic hardeners such as.

The photographic material of the present invention may contain various emulsion stabilizers such as azaindene compounds and phenylmercaptotetrazole, antifoggants, and the like. In addition, there are various additives necessary to obtain photographic materials, such as silicon, fluorine-containing compounds, surface modifiers such as aliphatic esters, etc.
It may contain various couplers, dyes, plasticizers, etc. in color photosensitive materials.

The photographic materials according to the present invention include ordinary black-and-white photographic materials (for example, black-and-white photographic materials for X-ray, black-and-white photographic materials for printing, etc.), ordinary multilayer color photographic materials (for example, color reversal films, color negative film, color positive film, etc.), and various photographic materials.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below. Note that all percentages are by weight unless otherwise specified.

Example l Silver chlorobromide emulsion containing 7% gelatin and 5% silver halide (
50 mol% of silver chloride) and 1 exemplified compound per kg of the emulsion.
0.2g of polyethyl acrylate latex with a particle size of 0.05μm (solid content 20% by weight)
) were added respectively. 50% of this photographic emulsion on baryta paper
It was coated by the ditub method at a coating speed of m/min and cooled and set. 2.5% gelatin solution 1 on top of this? Exemplary compounds 2, 4, 6, 8, 11.15 were added to 19 and 0. (i57zmcQ57) A gelatin solution containing polyethyl acrylate latex troy (solid content 20% by weight) was coated, cooled and set, and then dried. There were no bubbles or repellents, and the coating could be applied uniformly at a coating speed of 50 μ/min.Also, when these samples were developed with a regular metol-hydroquinone developer, the photographic properties (sensitivity, gamma, fog) were improved. ) had no adverse effects at all.

Example 2 A high-sensitivity high-contrast emulsion containing 5% gelatin and 6% silver iodobromide (silver iodide 1.5 mol%) was prepared. Exemplified compound 3 was added to this photographic emulsion as a 2% aqueous solution so that it was contained in the range of Q, 01y -2,59 per tKv of the emulsion, and 150g of polyethyl acrylate latex (solid content 2.
0% by weight) was added. This emulsion was coated on a cellulose triacetate support with a subbing layer and dried. As shown in Table 1, it can be seen that as the amount of Exemplary Compound 3 added increases, the number of repellents decreases significantly. It is also seen that even if the emulsion is a high-sensitivity, high-contrast emulsion, it has good photographic properties without fogging.

Table 1 Example 3 Antihalation containing a water-soluble magenta dye, gelatin and an ethyl acrylate polymer prepared according to the following formulation (1) on one side of a polyethylene terephthalate support having subbing layers on both sides 19. 5 mol% silver bromide,
3-carboxymethyl-5-[2-(3-ethyludiazolinylidene)ethylidene] in a matured high contrast silver halide emulsion containing 80 mol% silver chloride and 0.5 mol% silver iodide. rhodanine, 4-hydroxy-1,3,3a
,? -Tetrazaindene, mucochloric acid, polyoxyethylene nonylphenyl ether containing 50 ethylene oxide groups and N-(γ-diethylaminopropyl)-
After adding N'-phenylurea in the usual amounts, it was divided into two equal parts, and the first part was further divided into four equal parts. The dispersion was added to emulsion IKf at 20 hN and mixed well with stirring. 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 at a rate of 55.+-.5.9 silver per 100 m".

Prescription (1) Ethyl acrylate LK9 and 1009 of Exemplified Compound 8 of the present invention as a dispersant were added to Eirisu Water 12Q, and 500 to 8
Stir at 00 rpm to emulsify. Next, 0.159% of potassium persulfate as a polymerization initiator was added and heated while stirring.
Keep at 0-100°C. If the reaction is continued for 6 hours, the polymerization is completely completed. If steam distillation is carried out for 1 hour to remove some residual monomer, the desired stable aqueous dispersion of ethyl acrylate polymer can be obtained.

The solid vinyl polymer particles in these dispersions had a 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 2.

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

Surfactant (b) Prescription (4) In place of Exemplary Compound 2, sodium dodecylbenzenesulfonate (abbreviated as C9DS) was used, and the same procedure as Prescription (1) was followed.

Exemplary compound 8, the above surfactants (a) and (b) and SDS were added to a 6% gelatin aqueous solution on each coated emulsion layer.
are loOm for 1 to 9 aqueous gelatin solutions, respectively.
A protective layer was prepared by applying the coating liquids containing g in the combinations shown in Table 2 to a dry film thickness of 1 μm.

Using a tungsten light source for each of these sample films,
172 of each sample area was exposed through a 150-line magenta contact screen, and the remaining 1/2 was exposed to a light wedge without passing through the screen.
Development processing was carried out at 25° C. for 2 minutes using (1) and (2).

After development, the photographic sensitivity of each sample was measured, and the magnification was 10.
The dot quality was observed using a 0.0 optical microscope. The scratch strength of the film film during the development process was also measured. The results are also shown in Table 4.

Removed Table 3 in the margin Developer prescription [Sensitivity] Optical density 1.50 The reciprocal of the exposure amount of fog (with the control set as 100, expressed as relative sensitivity to that) [Stability of latex] KNol with polymer latex 40ta (0.2 in l
99 and 0.59 were added, and the state of aggregation after standing for 3 hours was evaluated (visual judgment).

A: No change B: Cloudy C: Coagulated matter D=
Slurry [Dot quality] 50% halftone dots were observed and visually graded as A-D.

A: Excellent B: Practically acceptable C: Inferior
D: Very poor [scratching strength] After developing, fixing, and rinsing in the above processing steps, the film surface is scratched with a weighted metal needle while immersed in the rinsing water. E1 (scratching strength) was determined.

As is clear from Table 4 (below), the photosensitive material containing the compound of the present invention and the polymer latex exhibits almost the same sensitivity in both developing solutions (1) and (II) with different ionic strengths. That is, the dependence on the developer is small.The polymer latex emulsion polymerized using the compound of the present invention is stable in the presence of an electrolyte, and the change in sensitivity due to the addition of the electrolyte is small. The comparative sample has poor polymer latex stability and poor halftone dot quality in lithographic development.

Also, the scratch strength is low.

Applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment May 220, 1986

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, at least one of the hydrophilic colloid layers has a 2-hydroxy-3-sulfopropyl group (containing a salt). 1. A silver halide photographic material comprising a polymer latex and a polymer latex.