JPH0223332A - Production of silver halide emulsion - Google Patents

Abstract

PURPOSE:To make it possible to disperse a photographic additive in the silver halide emulsion without remaining the coarse particle of the emulsion at the time of dispers ing a recrystallized crystal in the emulsion, and to prevent the generation of a coating trouble by being existed said additive together with a photographic additive which has a good dispersibility against water, at the time of dispersing the recrystallized crystal in the emulsion. CONSTITUTION:A water-insoluble photographic additive is dissolved in a solution which is incorporated a surfactant having -SO3 or -OSO3 group as a hydrophilic group, in an org. solvent belonging to alcohols, and then the obtd. solution is dropped into the water to recrystallize the additive. Next, the recrystallized additive is dispersed in the water contg. an another photographic additive which has the good dispersibility against the water with a dispersing device. The obtd. dispersion is incorporated in the silver halide emulsion. For example, the dispersion is carried out in the solution 2 to be dispersed which is enclosed in a tank 1 using a rotary agitator having a dissolver blade 3. Thus, the photographic additive can be incorporated in the silver halide emulsion, and the generation of the coating trouble is prevented without remaining the coarse particle of the emulsion at the time of dispersing the recrystallized particle in the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a silver halide photographic emulsion. In particular, it relates to a method of obtaining desired photographic performance by dissolving a substantially water-insoluble photographic additive in a small amount of a mixed solution of an organic solvent and a surfactant and adding the solution to a silver halide emulsion.

(Prior Art) Conventionally, as a method of adding various water-insoluble photographic additives to silver halide photographic emulsions, the photographic additives are dissolved in an organic solvent and dissolved in water or an aqueous solution containing an anionic surfactant. (e.g., Japanese Patent Application Laid-Open No. 11419/1982), or a method in which a solution of the photographic additive dissolved in an organic solvent is added and dispersed in an aqueous solution or a hydrophilic colloid solution containing an aqueous binder (e.g., US Patent No. 3
Specification No. 78857, Specification No. 3,660,101 1 Japanese Patent Publication No. 49-46416, Japanese Unexamined Patent Publication No. 49-128
No. 725).

[Problems to be Solved by the Invention] However, in these methods, the method of adding an organic solvent solution in which a photographic additive is dissolved into water or an aqueous solution containing an anionic surfactant requires re-contamination during addition. Crystallization occurs, and some photographic additives do not disperse the recrystallization, leaving coarse crystals (20 to 50μ) as they are. When added to silver halide, photographic additives such as spectral sensitizers The problem is that the time required for adsorption of the emulsion to the silver halide becomes longer, and therefore photographic sensitivity cannot be obtained within a short time, and furthermore, even if such an emulsion is coated, coating failures are likely to occur due to deposits etc. There was a point.

In addition, in the method of adding and dispersing a solution of a photographic additive dissolved in an organic solvent into an aqueous solution containing an aqueous binder or a hydrophilic colloid, recrystallization occurs when adding the solution as described above, but Hydrocolloid has a high viscosity, so it has good dispersion efficiency, but the power required for dispersion is large, and the foaming during dispersion becomes large, and coarse crystals trapped in the bubbles remain and cause coating failures. The problem was that it was easy.

In order to solve the above-mentioned problems, the applicant first added a surfactant having -SOs and -05Os as hydrophilic groups to an organic solvent belonging to alcohols, a substantially water-insoluble photographic additive. A method for producing a silver halide emulsion, characterized in that silver halide is dissolved in a mixed solution and the solution is added to the emulsion, and in the method, a small amount of base or base is added to the mixed solution. and acid have been added,
A method for producing a silver halide emulsion is proposed, which is characterized by dissolving a substantially water-insoluble photographic additive.

These inventions are excellent methods, but depending on the nature of the photographic additive, if a solution containing the photographic additive is dropped into water and recrystallized, the crystals may not form in water or in an aqueous solution. Some of them were not dispersed in aqueous solutions and hydrocolloids containing binders.

The purpose of the present invention is to solve the above-mentioned problems, to perform dispersion without leaving coarse particles in the dispersion of recrystallized crystals, and without causing aggregates or destruction of emulsions. An object of the present invention is to provide a method for producing a stable silver halide emulsion.

Another object of the present invention is to provide a manufacturing method in which the solution of the photographic additive added to a silver halide emulsion is a dispersion liquid that is free from precipitation and decomposition and has excellent stability over time.

(Means and effects for solving the problem) As a result of intensive study on this problem, the inventors of the present invention found that by coexisting with a photographic additive that has good dispersibility in water during dispersion, the dispersion of young children can be reduced. The present invention was based on the discovery that the dispersion of objects can be maintained.

That is, the above object of the present invention is to add -803. to an organic solvent belonging to alcohols as a hydrophilic group. A substantially water-insoluble photographic additive is dissolved in a solution in which a surfactant having a -05Os group is added and mixed, and the solution is dropped into water to recrystallize it. This is achieved by a method for producing a silver halide emulsion, which is characterized by adding other photographic additives with good dispersibility to the silver halide emulsion, dispersing it in a dispersing machine, and adding the dispersion to the silver halide emulsion. Ru.

In the present invention, other photographic additives with good dispersibility in water are added to water after being dropped into water for recrystallization. It has good dispersibility and can be mechanically dispersed in an aqueous solution system without the use of organic solvents or wetting agents or dispersants.

By coexisting with these and dispersing, the dispersion of the dispersible photographic additive is promoted.

In the present invention, dispersing with a dispersing machine means, for example, as shown in FIG.
This means using a 90m stirrer.

The daysilver blade 3 is connected to an impeller 31 as shown in FIG.
Vertical upward wing t! 133. It has many sets of vertical downward blades 32 alternately.

The ratio between the impeller diameter and the tank inner diameter is about 1:5 to 2:5, the ratio between the impeller diameter and the distance between the bottom of the tank and the impeller is about 2:1 to 1:1, the impeller diameter and the static liquid in the tank The ratio to depth is preferably about 1:3.

To explain the present invention in more detail, the substantially water-insoluble photographic additives that can be used in the present invention are solid additives, and specifically include the following. Spectral sensitizing dyes, antifoggants, color couplers,
Dyes, sensitizers, hardness19. agents, ultraviolet absorbers, antistatic agents, brighteners, desensitizers, developers, anti-fading agents, mordants, etc.

For more information on these additives, please visit RE! 5EAPCI(DT
SCLO-3IJRIE vol, 176 RD-17
643 pages 22-31 (December 1978
)It is described in.

For example, examples of the spectral sensitizer include methine dyes and styryl dyes such as cyanine dyes, merocyanine dyes, hemicyanine dyes, rhodacyanine dyes, oxonol dyes, and hemioxonol dyes. Among these dyes, anionic dyes such as dyes having one, preferably two or more sulfo groups or sulfoalkyl groups as substituents are effective.

As the spectral sensitizer, in addition to the above-mentioned publications, those described in the following publications can be used. German patent 9290
No. 80, U.S. Patent No. 2493748, U.S. Patent No. 2503776
No. 2519001, No. 2912329, No. 36
No. 56959, No. 3672897, No. 3694217
No. 4025349, No. 4046572, No. 26
No. 88545, No. 2977229, No. 3397060
No. 3522052, No. 3527641, No. 36
No. 17293, No. 3628964, No. 3666480
No. 3672898, No. 3679428, No. 37
No. 03377, No. 3814609, No. 3837862
No. 4026707, British Patent No. 1242588,
No. 1344281, No. 1507803, Special Publication No. 1977
-14030, 52-24844, 43-49
No. 36, No. 5312375, JP-A-52-11061
No. 8, No. 52-109925, and No. 50-80827.

Examples of substances other than spectral sensitizers include the following. That is, benzotriazole compounds,
4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, cationic polymers, chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucohalogen acids, Nitroindazoles, triazoles, benzotriazoles, benzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, tetraazaindenes, 5-pyrazolone couplers, pyrazolone benzimidazole couplers, acylacetamide couplers, naphthol couplers, phenol couplers, etc. be able to.

The amount of the substantially water-insoluble photographic additive added to the silver halide emulsion cannot be determined unambiguously depending on the type of additive and the amount of sI halide, but it can be added by conventional methods. Approximately the same amount can be used.

Particularly, the present invention is effective when the water-insoluble photographic additive is a photographic spectral sensitizing dye belonging to cyanine dyes excluding anionic dyes.

For example, surfactants having a group of 108O* include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, sulfosuccinate ester salts, and the like as anionic activators.

for example (Hereafter, this will be referred to as dye A) can be mentioned.

Organic solvents belonging to alcohols used in the present invention include aliphatic saturated alcohols, aliphatic unsaturated alcohols, alicyclic alcohols, aromatic alcohols, heterocyclic alcohols, and in particular aromatic primary alcohols and halogenated alcohols. Alcohol is preferred.

For example, benzyl alcohol (CatlsCHzOH)
(hereinafter referred to as solvent B) and fluorinated alcohol (hereinafter referred to as organic solvent C).

-3Oz as a hydrophilic group used in the present invention.

can be mentioned.

In the present invention, a solution in which a surfactant having a hydrophilic group of -3Os or -08O3 is added to a solvent belonging to alcohols is a solution in which both the organic solvent and the surfactant are mixed, although it differs depending on the type of the organic solvent and the surfactant. When dissolving with a mixed solution, the amount of surfactant is 25 to 100% by weight based on the amount of photographic additive, and the amount of organic solvent is about 173 to 100% by weight of the amount required for dissolving with organic solvent alone. Only 1/2 the weight.

In the present invention, a small amount of a base or a base and an acid may be added to the mixed solution of the organic solvent and the surfactant.

In the silver halide emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, etc. may be used as the silver halide.

The grain size of silver halide is not particularly limited, but it is 3
It is preferably less than μ. These silver halide emulsions can be easily prepared by the method described in the following literature. Chi-mie e by P. Glafkidea
t Physique Photographique
(Paul Monte1, 1967), G
, F. DuffIn Photo8rahic Bpa
-ulsion Chemistry (The Fo
Cal Press, 1966), V, L,
Making and by Zelilvan et al.
CoatingPhoLographic Emul
sion (The Focal Press, 196
4 years), etc.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed under an excess of negative ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Various other additives can be used in the silver halide emulsion used in the present invention. In other words, sensitizers such as sulfur sensitizers, reduction sensitizers, and noble metal sensitizers, stabilizers, surfactants, hardeners, thickeners, dyes, ultraviolet absorbers, antistatic agents, and brighteners. , a desensitizer, a developer, an anti-fading agent, a mordant, etc. can be used. Furthermore, a coupler such as a color coupler can also be used by dispersing it in oil.

With these additives, Ill! 5EARCHII
TSCLO-3URE (RD-17643), vol.
, 176, Pages 22-31 (Dec-embe
r 1978), THET)tEO1? Y OF T
HE P)IOTOGIIAPHIcPROCESS
(4th Ed,) Edited by T. H. James (19
77, M-acmillan Publishing
Co, Inc.) etc.

The binder used in the silver halide emulsion of the present invention is preferably gelatin, but in addition to gelatin, derivative gelatin such as phthalated gelatin, albumin, agar, gum arabic, cellulose derivatives, polyvinyl acetate, polyacrylamide, polyvinyl alcohol etc. are used.

The method for producing the silver halide emulsion in the present invention includes:
First, for example, a weighed amount of organic solvent is placed in a tank, a surfactant is added thereto, and the mixture is stirred and dissolved using a stirring blade at room temperature. The stirring blade is a turbine blade equipped with four blades on the stirring shaft, and the ratio of its diameter to the tank inner diameter is l:5~2=
5, the ratio of the diameter of the turbine blade and the gap between the bottom of the tank and the turbine blade is about 2:I to 1; the ratio of the diameter of the turbine blade to the depth of the static liquid in the tank is 1:1 to 1. ; It is preferable to set it to about 3. However, in this case, the stirring blades are not limited to turbine blades, and paddle blade propeller blades, day silver blades, etc. may also be used.

If you wish to adjust a small amount, you can use a magnetine cooler. Depending on the type of surfactant added, a small amount of a base or a base and an acid may be added.

Next, once a stirred mixture is prepared, the mixture is heated to 70°C, and then photographic additives are added thereto and dissolved at 70°C with stirring as described above. After confirming that it is completely dissolved,
Stirring is stopped, the solution is cooled to 40-50°C, and the solution is dropped into water under stirring to recrystallize. In that case, a Daysilver blade is used as the stirring blade.

Recrystallization is when photographic additives are converted into organic solvents that are good solvents)
When a dissolved substance is added to water, which is a poor solvent, its concentration exceeds its solubility (saturation concentration or higher) and crystals precipitate.

Next, other photographic additives with good dispersibility (or more than one) are added to the aqueous solution without adding an organic solvent, a wetting agent, or a dispersant, and dispersed using a high-speed stirrer. In this case, photographic spectral sensitizing dyes belonging to anionic cyanine dyes can be mentioned as other photographic additives with good dispersibility.

A typical example of this is, for example, as mentioned above, by coexisting and dispersing a highly dispersible pigment with a well-defined molecular structure and a substantially water-insoluble pigment, it is possible to reduce the dispersion of young children. Dispersion of things is promoted.

It goes without saying that photographic additives with good dispersibility can be added simultaneously with photographic additives that are substantially insoluble in water.

As mentioned above, the high-speed stirrer used as a dispersion machine has a dispersion time of 60 to 180 minutes9.
Preferable conditions are a dispersion temperature of 50'C and a pue of s~7.5. Through this dispersion, the recrystallized particles are dispersed to a size of 1 μm or less.

The solution obtained in the present invention may be added directly to a silver halide emulsion, or may be added in a dissolved state or in a gel state after being mixed with a protective colloid. can be obtained.

〔Example〕

One embodiment of the present invention will be described. However, the present invention is not limited to this embodiment.

To 10 g of benzyl alcohol as an organic solvent belonging to alcohols, add 0.8 g of a surfactant Di having a -3 (h group) as a hydrophilic group, add a small amount of triethylamine 0.1 g as a base, and 0.1 g of acetic acid as an acid, and let the mixture cool at room temperature. A solution was prepared by stirring and dissolving under the following conditions, and 1.59 g of the above-mentioned dye A was added to the solution as a water-insoluble photographic additive.
The mixture was heated and dissolved at 70°C for 10 minutes using a magnetic stirrer to prepare a solution. After complete dissolution, stirring was stopped and the mixture was cooled to 50°C.

The solution was dropped into water, and the recrystallized particles were dispersed as follows.

Comparative Example-1 The above solution was added dropwise to 500 ml of water for 10 minutes, recrystallized, adjusted to pH 7, and then dispersed at 50°C for 120 minutes using a high-speed stirrer at 3000 r, p, m. However, as a result, it could not be dispersed.

Comparative Example-2 The above solution was added dropwise to a 2wX gelatin aqueous solution of 500ml over 10 minutes to create recrystallization, adjust the pH to 117, and perform dispersion at 50'C for 120 minutes. As a result, dispersion was not possible and foaming was large.

Example-1 The above solution was added dropwise to 500 ml of water for 10 minutes to create recrystallization, and 8.12 g of the above dye B as a photographic additive with good dispersibility was added to the liquid. 0.3
g, adjusted to pH 7, then adjusted to 3.0 with a high-speed stirrer.
When dispersing for 120 minutes at 00r, p, m, 1
It was possible to disperse into particles smaller than μm. When this was added to a silver halide emulsion and coated, no coating failure occurred and the photographic performance was excellent.

〔Effect of the invention〕

As described above, by combining and dispersing the silver halide emulsion of the present invention with additives having good dispersibility, conventional photographic additives with poor dispersibility could not be added to silver halide emulsions. Photographic additives can now be added to silver halide emulsions, without leaving coarse particles in the dispersion of recrystallized grains, without generating aggregates, without destroying emulsions, and without causing coating failures. It became possible to produce stable silver halide emulsions.

In addition, the amount of organic solvent and surfactant used to dissolve photographic additives can be significantly reduced, resulting in the formation of precipitates.

We were able to create a dispersion that did not decompose and had excellent stability over time.

[Brief explanation of the drawing]

FIG. 1 is a schematic side view of a high-speed stirrer used for dispersion according to the present invention, and FIG. 2 is a perspective view of a day silver blade. 1... Tank 2... Liquid to be dispersed 3...
Daysilver 31... Impeller 32.33...
feather

Claims (1)

[Claims] -S as a hydrophilic group in organic solvents belonging to alcohols
A substantially water-insoluble photographic additive is dissolved in a solution in which a surfactant having a group O_3, -OSO_3 is added and mixed, and the solution is dropped into water for recrystallization, and then A method for producing a silver halide emulsion, which comprises adding other photographic additives with good dispersibility in water to the water, dispersing it with a dispersion machine, and adding the dispersion to the halide emulsion. .