JPS58149037A - Manufacture of photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To manufacture a fine-grained photographic emulsion with high single dispersibility, high sensitivity and high contrast in a short time by mixing an aqueous soln. contg. ammonium ions, halide and a hydrophilic colloidal with an aqueous soln. of ammoniacal silver nitrate and an aqueous soln. of acidic halide by a simultaneous mixing method at 8.0-9.0pH to form silver halide crystals and to regulate the grain size of the crystals to 0.15-0.30mum. CONSTITUTION:A liq. mixture prepared by said simultaneous mixing method is kept at a high silver ion concn., so it is important to controll the pH value. When the pH value is increased, the internal sensitivity and internal fog are increased, and the surface sensitivity is reduced. The pH value is adjusted during the formation of silver halide crystals so that it converges on a desired range while keeping the silver ion concn. high. Silver halide crystals are formed at 8.0-9.0pH during mixing, and the grain size of the formed crystals is regulated to 0.15-0.30mum. A photographic silver halide emulsion with high sensitivity and high contrast can be obtd. using the silver halide crystals having 0.15-0.30mum grain size.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a silver halide photographic emulsion using the IWJ time mixing method. In particular, the present invention relates to a method of manufacturing a silver halide photographic emulsion which has fine grains, high sensitivity, and high contrast by an ammonia method.

Generally, silver halide photographic emulsions are manufactured by the following steps. That is, it is roughly divided into (physical ripening including precipitation and grain growth of IJ silver halide grains, (2) removal of excess salts and generated salts, (3) chemical ripening, +4111m cloth, and drying process.

Usually, the first step is to prepare nitrate #kIil! in a solution of a protective colloid such as gelatin. The solution is mixed with an OT-soluble halide solution, and physical ripening is continued while maintaining the lagoon until the desired silver halide grain size is obtained. Rarely, only one soluble halide is used in this step, or may a mixture of two or IIIA halides be used.

Technology for increasing the sensitivity of silver halide emulsions has been studied from time to time, but there is still room for further research. For example, halogenated particles can cause surface accumulation and/or damage due to stray light.
Or form an inner me.

The surface latent image is bounded by a regular developer, giving a grade of 9, but is not agglomerated by the internal fII. For this reason, for example, in negative-working silver halide milk steel, the sensitivity loss is large and the sensitivity is low compared to the surface latent image type υ silver halide grains, which tend to form internal f#I images. t-
Not good.

Silver halide emulsion I with high surface sensitivity and low internal sensitivity KO
As a conventional technique for the II manufacturing method, the following technique is known. That is, as a method for producing &I& degree silver halide photographic powder in a short time, the growth of silver halide grains such as ammonia is promoted.41! It is important to use compounds that are

-10,000, In order to produce cubic crystal grains consisting of only (100) planes in the growth of silver halide grains, a low
It is known that it is possible to grow silver halide grains under Ag value conditions. However, under low pAg value conditions, capri, which is unfavorable in terms of photographic properties, is generated, and this precipitate is a problem of soil use. In order to achieve a level without
It cannot be made into Ag value. In addition, at pAg values near the molarity points of silver ions and halide ions, 1i of the pAg value
4, relatively high pAgrt when producing particle tubes consisting only of (100) planes, as III@ becomes unstable in non-rich areas.
pAgA such that some (111) plane particles are generated at i
The reality is that there is no way to create a g-ray region.

However, the presence of ammonia in the prior art makes silver halide grains produced by the neutral method [compared to pA
Even in the high g region (100), long-lasting particles are generated. Furthermore, if silver halide grains are grown in a region where pAg is considerably low due to the presence of ammonia, twin crystals with (100) curvature are formed;
If it is too high, twins with (111)m will be formed.

Since twin crystals in the form of superimposed dodecahedral crystal grains have a tlt length to become coarse grains, the occurrence of twin crystal grains results in an emulsion with a significantly wide grain distribution, which is unfavorable in terms of photographic properties.

These things are described by W. Morcocki and A. 2'ale.
Photographic 5
science and engineering) M
17, No. 289-294j4 (1973).

Preferred monodisperse emulsion 1r! 11! To create, twin ai
A non-crystalline O particle that does not have oi, or even if it has a twin plane, is a particle in which one particle size is not particularly larger than other particles, which is superposition.

Methods for preparing homogeneous monodisperse emulsions are already known from the literature by Hashira, but most of them involve preparation methods in the halide ion excess region. The region in which monodisperse emulsions are superior on this side with an excess of light ions is limited to a narrow region around equimolar and axially unstable. In other words, due to a slight increase in excess niolide ions ak, crystal fi
l changed from a cube to a 14-metal body, then to an octahedron, and then to a twinned polydisperse emulsion. Many documents have clarified that photographic properties differ greatly between these crystal habits. Therefore, even if it is possible to prepare the product Q) with an excess of halide ions from an experimental plan, it is not suitable for continuing stable industrial production.

NTJ h own using VC ammonia, one shot from the particle chairman's meeting promotion, #! When producing an L emulsion, there are often some difficulties associated with this process. The reason for this is that ammonia is added to the silver nitrate aqueous solution and halide aqueous solution used in general physical ripening, so ammonia grains thicken significantly during crystal growth, and the particle size distribution becomes wider due to Ostwald ripening. Therefore, a bath liquid must be added to control ammonia leakage. The halogenated particles produced under such harsh conditions are
1=5-1 grains were formed, and the monodispersed emulsion with a narrow particle size distribution as expected was not produced.

A first object of the present invention is to produce a fine-grained, monodisperse cylindrical photographic emulsion.

The second object of the present invention is to provide a photographic emulsion with extremely high contrast.
It is to manufacture.

The third object of the present invention is to achieve industrial production in a short period of time.
The above object of the present invention is to produce a monodisperse dark photographic emulsion. When mixed by the simultaneous mixing method, halogenated crystals are produced when the pH during the reaction is in the range of 8.0 to 9.0, and the halogenated sweetfish crystals are 0.15 mm to 0°30 μm CDkFjM. An aqueous solution containing L ammonium ions, a halide and a fresh water-based colloid (hereinafter referred to as mixed Ammonium ions (referred to as liquids) are supplied in the form of aqueous ammonia or in the form of ammonium salts such as ammonium bromide, ammonium chloride, ammonium iodide, and ammonium nitrate.
1 water or an aqueous ammonium salt. The concentration Ij of ammonium ions in the liquid mixture is arbitrary, but preferably 0.005 to 1.07 l/l, and %IC0,
05 to 0.60 mol/L is preferable.

Examples of the halide in the mixture include chlorides such as potassium chloride and sodium chloride; monobromides such as potassium bromide and sodium bromide; and monoiodides such as potassium iodide and sodium iodide. , these halides may be used alone or in combination with 21a or more. And halide v@flu in the mixture
0.001 to 1.0 mol/t fl L,
Particularly preferred is K O, 005 to 0.255 7 l/l.

The releasing halide water bath solution is a halide aqueous solution made pHt-acidic, and the halide is heated @ vc
A halide similar to that used for PFU is used, and to make this aqueous solution acidic, it can be added to an organic acid, an organic acid, and a suitable Il'.

Any acid can be used, but it is preferable that it does not adversely affect the photographic properties, and acetic acid and sulfuric acid are particularly preferable. The rice used in the acidic halide aqueous solution is preferably 11,050% to 90%, which completely neutralizes the ammoniacal silver nitrate, and the pH of the mixture is in the range of 8.0 to 9.0. Ru.

Ammoniacal nitrate 12 silver water 11 used in the present invention! In the solution, some or all of the silver ions used are used as an ammoniacal silver complex salt, but preferably all are used as an ammoniacal nitrate complex salt.

The simultaneous mixing method in the present invention includes a method in which an ammoniacal silver nitrate aqueous solution and an acidic halide aqueous solution are added into the mixed solution at the same time.
Although it does not have to be stirred, it is best to pour it under stirring.

Regarding this 1N8 mixed method, see T.H. James (T. H.), The Q Theory Op Photographic Process (The Theor.
yof Photographic Proesa)
4th edition, pages 88-104.

The pH of the mixed solution is determined by the amount of the ammoniacal silver nitrate aqueous solution and the acidic halide aqueous solution mixed, and the pFI value thereof is in the range of 8.0 to 9.0.

In the simultaneous mixing method of the present invention, since the mixed solution maintains a high silver ion concentration, the pH value can be easily controlled. p
As the H value increases, the internal sensitivity and internal m fog become flat.
1. Surface sensitivity decreases. During the process of forming 1 ml of halogenated particles, the pH value is adjusted so as to converge within a desired range while keeping silver ions -11 high. pH during mixing is 8
．． When the value falls below 0, m[ of the produced silver halide crystal grains is considerably lower than the desired sensitivity.

Also, the pH during mixing was 9. When the value exceeds O1, the desired 'fx hardening cannot be ignored because of the gradation properties of the produced silver halide crystal grains. In the present invention, silver halide crystals are produced when the pu during mixing is in the range of 8.0 to 9.0, and the produced #IM halide crystal grains have a grain size of 0.15urn to 0°3Qam. A silver halide photographic condenser with high sensitivity and high contrast can be obtained with such a grain size adjusted as described above.

The ammoniacal silver nitrate aqueous solution and the acidic halide aqueous solution should be added at a rate commensurate with the speed of growth of the silver halide crystal grains.

Silver halide photographic hole tljk provided by the present invention
Examples of the silver halides that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide, and mixtures thereof.

As the hydrophilic colloid used in the present invention, gelatin is most preferable, but other materials may also be used as necessary, such as derivatized gelatin, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives, acrylamide, imidized polyacrylamide, and casein. , vinyl alcohol polymer,
It can be used in combination with polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and hydrolyzed polyvinyl acetate.

The silver halide photographic aperture 41 of the present invention is made of various known chemical sensitizers, spectral sensitizing steel, anti-capri, high-contrast steel, hard gelatin II, surfactants, conversion property improving agents, thickeners, nets, etc. It may contain additives for point-improving steel parts. Examples of the above-mentioned various additives include noble metal sensitized steels such as d1 active gelatin, water-soluble gold salts, water-soluble platinum salts, water-bathable palladium salts, water-soluble rhodium salts, and water-soluble iridium salts. Sensitization; sulfur sensitization; selenium sensitization; polyamine, tin chloride chemical sensitization. Can be chemically sensitized alone [4] or in combination with chemically sensitized steel such as SCI@轡. .

There are no particular restrictions on the spectral sensitizer, such as zeromethine dyes, monomethine dyes, dimethine dyes, cyanine dyes of trimethine dyes, or spectral sensitizers of melonani7 dyes. It can be sensitized to

These techniques are described in U.S. Patent No. 2,688,545.
No. 2,912,329, No. 3,397,06
No. 0, No. 3,615,635, No. 3,628,9
Specification No. 64, British Patent No. 1,195,302, British Patent No. 1.242,588, British Patent No. 1.293,862, West German Patent (OLS) No. 2,030,326, British Patent No. It is also described in the specification of No. 2,121,780, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 44-14030, etc. The selection depends on the wavelength range to be sensitized, the sensitivity, etc., the purpose of the photosensitive material,
It can be arbitrarily determined depending on the purpose.

The emulsions of the invention may contain other additives. For example, abindenes, triazoles, tetrazoles,
Stabilizers and antifogging agents such as imidazolium salts, tetrazolium salts, and polyhydroxy compounds? @: Aldehyde type, aziridine type, inoxazole type, vinyl sulfone type,
#II of acryloyl type, albodiimide type, maleimide thread, methanesulfone ester type, triazine type, etc.
Cutting: Benzyl alcohol, polyoxyethylene compound movement 'fA image promotion cutting; Kuroman yarn, Claman thread, bisphenol type, phosphite type mi*cii: Sadatsugu; Wax, glyceride of higher fatty acids, higher fatty acid There are higher alcohol esters such as IIIiIIIiI4.

In addition, it is used as a coating aid as a surfactant, as a permeability improver for processing liquids, as an antifoaming agent, and as a rounding material for controlling various physical properties of photosensitive materials.
A variety of cationic, nonionic, and amphoteric materials can be used. As antistatic materials, diacetyl cellulose, styrene (-fluoroalkyl rhidium maleate copolymer), styrene-maleic anhydride copolymer, and -Alkali salts of reactants with amine benzenesulfonic acid are effective.Additionally, as latexes to be added to improve the material properties, acrylic esters, vinyl esters, etc. and other monomers with ethylene groups are effective. Copolymers of gelatin can include glycerin, glycol compounds, etc., and binders include styrene-maleic copolymers and alkyl vinyl ether-maleic acid copolymers. Examples include merging.

This silver halide photographic emulsion must be prepared by a subbing layer, an intermediate layer, etc., such as baryta paper, polyethylene seeded paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, etc. It is coated on a polyester film such as polyethylene terephthalate or a support such as polystyrene by a known method.

The silver halide photographic material to which the present invention can be applied may be either a black-and-white photographic material or a color photographic material, and can be used for various purposes such as general use, printing use, xlii use, and radiation edge use. .

The silver halide photographic light-sensitive material produced by the method described above may be exposed to short-time or flash light in addition to normal exposure.
Photo processing can be done in the usual way. Base.

The main photographic processing steps are a dust image step and a fixing step, and these two steps may be performed simultaneously.

The present invention will be illustrated below with actual examples, but the actual cram school style of this @ size is not limited to these examples.

Burmese example-1 Emulsion (1) of the present invention was produced as follows.

fII hoe) 501! Acetic acid aqueous solution 18-40℃
The above solutions (B) and (C) were mixed simultaneously for 10 minutes. p in this mixture
The H value was 8.5. This is used for neutralizing Owk.
) was added to form an emulsion (13t).The average grain size of the silver halide grains was 0.23 am '''
With C, the total particle size is ±21 of the average particle size.
The monodispersity was within the acceptable range.

Emulsion (2) was also prepared as follows for comparison.

Note that solutions (A) and (a) were the same as those of the present invention described above.

solution) 50% acetic acid aqueous solution 8- and t- were mixed in the same manner as in the above invention.

At this time, the pH during mixing was 7.0.

Furthermore, for comparison, emulsion (3) was produced as follows.

Note that Melt 1 (B) was the same as that of the present invention.

Solu* (050 aqueous vinegar solution 38- This t was mixed with the above-mentioned method of the present invention and Oka's method.

pH[ij] during mixing at this time was 10.0.

Emulsions (1), (2) and (3) were washed with water and chemically ripened by gold sensitization and sulfur sensitization, and then 4-hydroxy-6-methyl-1,3°31.
4. Add 7-chitrazaindene to 1 mol of silver halide.
Each was added so that OgK was obtained. Each milk Ili obtained in this way! lt polyethylene terephthalate film base. This sample was exposed to white light using a tK8-I11 sensitometer (*1 manufactured by Nishiroku Photo Industry Co., Ltd.), and then developed for 30 seconds at 35° C. in a dust cabinet having the following composition.

[Developer]

Since it was fixed, washed and dried by the usual method, the following table-1F
-I looked for sensitivity and force/ma like I did.

It was shown in

It is clear from the results in Table 1 that emulsion ill of the present invention has a higher sensitivity than comparative emulsions (2) and (3) and has a 6i! It can be seen that this is an emulsion made into words.

Claims (1)

[Claims] Water containing ammonium ions, halide, and hydrophilic colloid *tuc When the ammoniacal silver nitrate aqueous solution and the acidic halide aqueous solution are mixed by the simultaneous mixing method, the pH during the reaction is 8. Silver halide crystals are formed at a wheel load of θ~9.0, and skeleton silver halide crystals are formed at a wheel load of 0.15 am~0.
A method for producing a silver halide photographic emulsion characterized by having a grain size in the range of 30 am.