JPH02135437A - Preparation of silver halide emulsion - Google Patents

Abstract

PURPOSE:To stabilize a process for prepg. a silver halide emulsion by dispersing photographic additives into an aq. system, then adding a photographic additive which is insoluble in water but soluble in a surfactant to the liquid dispersion together with the surfactant. CONSTITUTION:At first, a substantially water-insoluble photographic additive is mixed with a surfactant having a hydrophilic group such as -SO3, -OSO3, and the liquid mixture is added to an aq. dispersion of a photographic additive having high dispersibility in water. Obtd. mixture of the liquid dispersion can be added to a silver halide emulsion without requiring addition of an org. solvent. Moreover, if the mixture of the liquid dispersion is added to a silver halide emulsion a silver halide emulsion of good quality is obtd. without causing generation of coagulated product, destruction of emulsified product, nor defects in a coating stage. Further, productivity of a silver halide emulsion is improved because several photographic additives having different dispersibility and insolubility in water or surface active agent can be dispersed to form one and same liquid dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION C. Industrial Application Field The present invention relates to a method for producing a silver halide photographic emulsion. In particular, a method in which a substantially water-insoluble photographic additive is dispersed in an aqueous solution of the photographic additive together with a surfactant without using any organic solvent, and then added to a silver halide emulsion to obtain desired photographic performance. It is related to.

[Conventional technology]

When adding various water-insoluble photographic additives to conventional silver halide photographic emulsions ■ Dissolve the photographic additives in an organic solvent such as methanol,
A method of adding the solution to a silver halide emulsion (for example, Japanese Patent Publication No. 50-40659, U.S. Patent No. 3.788,
Specification No. 857, Japanese Patent Application Laid-Open No. 11419/1983, U.S. Patent No. 3.660.101, Japanese Patent Publication No. 49/1983
Publication No. 416).

(2) A method in which a water-insoluble photographic additive is dissolved in an organic solvent, mixed with its condensate, and then the organic solvent is removed to form a dispersion in water (for example, JP-A-49-128725).

(2) A method of solubilizing a water-insoluble photographic additive with a surfactant and adding the solubilized solution to a silver halide emulsion (for example, Japanese Patent Publication No. 49-44895).

(2) A method in which a substantially water-insoluble photographic additive is mechanically dispersed in an aqueous system, and the resulting dispersion of the photographic additive is added to a silver halide emulsion (for example, in JP-A No. 52 −
110012, JP-A-53-102733, and US Pat. No. 4,006,025).

[Problem to be solved by the invention]

However, since the method (■) uses an organic solvent, it requires an amount of organic solvent that exceeds the solubility. Especially when using photographic additives that are poorly soluble in organic solvents, a large amount of organic solvent must be used. There are problems such as the formation of aggregates when adding the photographic additive solution or dispersion obtained by the above method to a silver halide emulsion, and the formation of lumps or streaks when coating a silver halide emulsion. There are problems such as coating failure.

Method (2) has the problem that the concentration of the photographic additive changes or decomposes during the process of removing the organic solvent (by evaporation or membrane separation), and has the disadvantage of complicating the manufacturing process.

Furthermore, method (2) has good dispersibility in water, but if a photographic additive that is insoluble in a surfactant is present in the same dispersion,
This has the problem that coarse crystals remain as they are and coating failures are likely to occur.

In addition, method (2) has good solubility in surfactants, but if photographic additives with poor dispersibility in water are present in the same dispersion, coarse particles remain as they are, and coating failures are likely to occur.

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to prevent the generation of aggregates and destruction of emulsions when adding water-insoluble photographic additives to silver halide, thereby preventing failures (clumps) during the coating process. It is an object of the present invention to provide a method for producing a silver halide emulsion that can be stably produced without causing any problems such as streaks, streaks, poor adhesion, etc.

[Means and effects for solving the problem] As a result of intensive study of this problem, the present inventors first developed a substantially water-insoluble photographic additive having a -50s, -05Ox group as a hydrophilic group. A dispersion obtained by mixing with a surfactant and adding the resulting solution to an aqueous dispersion of a photographic additive with good dispersibility in water can be added to a photographic emulsion without using any organic solvent. This fact was discovered and the present invention was developed.

That is, the above object of the present invention is to add a photographic additive with good water dispersibility to water, disperse it in a dispersion machine, and then add it to the dispersion liquid, which is substantially insoluble in water and soluble in a surfactant. Silver halide, which is characterized in that a photographic additive with a high oxidation rate is added and mixed together with a surfactant having -50s and -0503 groups as hydrophilic groups to form a dispersion, which is then added to a silver halide emulsion. This is achieved by an emulsion manufacturing method.

To explain the present invention in more detail, examples of photographic additives with good water dispersibility in the present invention include (hereinafter referred to as dye A).

Substantially water-insoluble photographic additives that can be used in the present invention include solid additives such as the following: 0 spectral sensitizing dyes, anti-capri agents, and color additives. Couplers, dyes, sensitizers, hardeners, ultraviolet absorbers,
Antistatic side, brightener, desensitizer, developer, antifading agent, mordant, etc.

For these additives, please refer to RESf! ARCHDIS
CLO5-FIRE vol, 176 RD-1764
3 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. 53-12375, JP-A No. 52-1106
No. 18, No. 52-109925: No. 50-80827
It is stated in each publication.

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-virazolone couplers, pyrazolone benzimidazole couplers, acylacetamide couplers,
Examples include naphthol couplers and phenol couplers.

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, the III halide, etc., but the amount added by conventional methods cannot be determined. Approximately the same amount can be used.

However, the present invention is effective in the case of photographic spectral sensitizing dyes belonging to cyanine dyes as photographic additives that are substantially water-insoluble and highly soluble in surfactants.

This tendency is particularly strong in betaine series.

As an example, CJs (Hereafter, this will be referred to as dye B) It is very effective.

The hydrophilic group used in the present invention is -5o! , −
Examples of surfactants having the group 05O1 include alkyl sulfates, alkyl sulfonates, and anionic surfactants.
Examples include alkylaryl sulfonates and sulfosuccinate ester salts.

Especially CHzCOOC)! xcH(CJs)CJqNaOsS
CHCOOCLCH(CJs)C4H1 is preferred.

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. Chimie et by P, GIafkides
Physique Photographique
(Paul Monte1, 1967), G.
Photographic Em-u by F. Duffin
lsion Chemistry (The Foca
Press, 1966), V, L, Zel
Making and C by iks+an et al
oatingPhotographic Emulsi
on (The Focal Press, 1964).

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 in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which 9Ag 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, exacerbating agents such as sulfur sensitizers, reduction sensitizers, and noble metal sensitizers, stabilizers, surfactants, hardeners, thickeners, dyes, ultraviolet absorbers, antistatic agents, brighteners, Desensitizers, developers, anti-fading agents, mordants, etc. can be used. Furthermore, a coupler such as a color coupler can also be used by dispersing it in oil.

For these additives please contact RESEARCHDISC
LO-5LIRE (RD-17643), vol, 1
76, Pages 22-31 (December 1
97B), THE THEORY OF THE P
H0TOGRAPHIC PROCESS (4th E
d,) T, H, Jaebes W (1977, Ma.
csillan Publishing Co, In
c,) etc. are specifically described.

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:
For example, first, as shown in Figure 1, a weighed amount of distilled water is placed in a tank 1, a photographic additive (sensitizing dye) with good dispersibility in water is added, and the temperature is 50'C. Stirring blade 3
The sensitizing dye is dispersed by stirring at high speed, and the sensitizing dye is
Dispersed below μ turtle.

The agitator is a day silver blade, and has a large number of vertically upward blades 33 and vertically downward blades 32 alternately arranged on an impeller 31, as shown in FIG.

The ratio of impeller diameter to tank inner diameter is l;5~2:5
The ratio of the impeller diameter to the gap between the bottom of the tank and the impeller should be set to about 2:1 to ti1, and the ratio of the impeller diameter to the depth of the static liquid in the tank should be set to about 1:1 to 1:3. This is desirable.

Next, once the dispersion liquid is prepared, the temperature of the dispersion liquid is kept at 50'C, and a photographic additive that is substantially water-insoluble and highly soluble in surfactants is added as a hydrophilic group of -5O3-O3Os. It is added together with a surfactant having a group and dispersed while stirring at low speed. After confirming that it is completely dispersed, the stirring is stopped and the dispersion thus obtained is added directly to the silver halide emulsion, or mixed with the protective colloid and then added in the solution state. Alternatively, sufficient photographic performance can be obtained by adding it in a gel state by mixing it with a protective colloid and then gelling it.

Preferred embodiments of the present invention include the following.

(1) In the claims, the substantially water-insoluble photographic additive and the highly dispersible photographic additive are halogenated photographic spectral sensitizing dyes belonging to cyanine dyes. Method for producing silver oxide emulsion.

C) In the claims or implementation example (1), the -
3Q3. A method for producing a silver halide emulsion, characterized in that the amount of the surfactant having the group -0SOs added is 150 to 500% by weight based on the amount of the photographic additive.

〔Example〕

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

Example-1 2.13 g of the above-mentioned photographic additive dye A, which has good dispersibility in water, was added to 1.21 g of distilled water, and the dispersion temperature was set to 5.
0°C PH6.5 to 7.5 Dispersion time 60 to 180 minutes The above-mentioned dye A was dispersed to a size of 1 μm or less by high-speed stirring with a Daysilver blade.

Next, 27.87 g of the above-described photographic additive dye B, which is substantially water-insoluble and highly soluble in surfactants, is added to the dispersion, and 27.87 g of the above-mentioned surfactant C4 having 1503 hydrophilic groups is added to the dispersion.
The dye B in the dispersion was completely dissolved by stirring at low speed with a Desilver blade for 10 to 20 minutes. The dispersion prepared as described above was immediately added to a silver halide emulsion to produce a photographic emulsion. It is possible to easily produce a stable silver halide emulsion without causing aggregates or destruction of the emulsion, and therefore without causing failures in the coating process (clumps, streaks, poor adhesion, etc.). done.

Comparative Example-1 2.13 g of the above-mentioned photographic additive dye A and 27.87 g of the above-mentioned photographic additive dye B were mixed with 1.1 g of distilled water.
21, dispersion temperature: 50°C, pH: 6.5 to 7.5, dispersion time: 180 minutes, using a dissolver blade for high speed stirring, but dye A was 1μ-
Dye B was not dispersed and the diameter was 10 μm.
Many of the following coarse grains remained and it was virtually impossible to add them to the silver halide emulsion.

Comparative Example 2 45 g of the surfactant C described above was added to 1.2 g of distilled water and dissolved at a temperature of 50°C, and the dye A described above was added to the solution.
...2.13g was added to the above dye B...27.87
The treatment was carried out using low speed stirring using a dissolver blade for 30 minutes at a temperature of 50° C. and a pH of 6.5 to 7.5 hours. Dye B was dissolved, but Dye A was poorly dispersed and many large particles remained.

I tried increasing the amount of surfactant C to 240 g, but the preparation results were the same and it was practically impossible to use.

Comparative example-3 The order of addition was reversed from Example-1.

That is, 27.87 g of the above-mentioned additive dye B for photography was added to 1.21 g of distilled water together with 41.82 g of the above-mentioned surfactant C, and the temperature was 50°C and the pH was 6.5 to 7.5. Dye B was completely dissolved by stirring at low speed with a dissolver blade for 10 to 20 minutes, and 2.13 g of the above-described dye A was added to this solution, and the dispersion temperature was 50゛CP)I 6.5 to 7. .5 Dispersion time: 60 to 180 minutes Dispersion was performed using Desilva blade stirring.

When stirring at low speed, dye A was not dispersed, and when stirring at high speed, there was a lot of foaming, resulting in insufficient dispersion of dye A, making it practically unusable.

In addition, there are photographic additives that have good dispersibility in water but are insoluble in surfactants, and photographic additives that are soluble in surfactant aqueous solutions.
Photographic additives with poor dispersibility in water can be made into the same dispersion liquid, greatly improving productivity.

[Effects of the Invention] As shown in the above examples, the present invention first mechanically disperses a photographic additive dispersible in an aqueous system in water, and then adds a substantially water-insoluble photographic additive to the dispersion. photographic additives with high solubility in surfactants as hydrophilic groups -so,,-
By adding and mixing together with a surfactant having a group called 03Os, dissolving it in the dispersion, and adding the dispersion to a silver halide emulsion, it is possible to prevent the generation of aggregates and the destruction of the emulsion. Therefore, failure in the coating process (clumps).

It was possible to easily produce a high-quality silver halide emulsion without causing streaks, poor adhesion, etc.

In addition, there are photographic additives that have good dispersibility in water but are insoluble in surfactants, and photographic additives that are soluble in surfactant aqueous solutions.
Photographic additives with poor dispersibility in water can be made into the same dispersion liquid, greatly improving productivity.

[Brief explanation of the drawing]

FIG. 1 is a schematic side sectional view of a dissolving/dispersing apparatus used in the present invention, and FIG. 2 is a plan view of a stirring blade. 1...tank 2...dissolution/dispersion liquid 3...
Daysilver 31... Impeller 32.33...
feather

Claims (1)

[Claims] A photographic additive with good dispersibility in water is added to water and dispersed with a dispersion machine, and then a photographic additive that is substantially insoluble in water and highly soluble in a surfactant is added to the dispersion. A method for producing a silver halide emulsion, which comprises adding and mixing together with a surfactant having -SO_3, -OSO_3 as a hydrophilic group to form a dispersion, and adding the dispersion to a silver halide emulsion.