JPS5948756A - Preparation of silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To enhance aging stability of a coating emulsion from the preparation of the emulsion to coating of the support, by adding at least 2 kinds of sensitizing dyes different in chemical structure to the silver halide photographic emulsion during its preparation separately at a different time. CONSTITUTION:A sensitizing dye A, such as formula I is added when chemical ripening is carried out by adding sodium thiosulfate, adenine, etc. to a silver halide emulsion. The intended silver halide photographic emulsion is obtained by adding a sensitizing dye B having a chemical structure different from that of the dye A after the chemical ripening before coating the support with the emulsion. As the sensitizing dye B, sensitizing dyes represented by formulae II and III are preferable in which Y1 is S, Se, or O; Y2 is S or Se; Z1, Z2 are each thiazole, oxazole, or the like; Z3 is benzothiazole, naphthothiazole, or the like; R1, R3 are each H or lower alkyl; R2, R5, R6 are each lower alkyl; X is halogen or acid anion; and l is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic emulsion that contributes to stabilizing the performance and quality of silver halide photographic light-sensitive materials. The present invention relates to improving the stability of the emulsion coating solution over time until it is applied onto the body.

In recent years, silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) have been processed using equipment to undergo photo-processing.
Various attempts have been made to maintain a uniform tithe and tl'' for dogs, despite the control gained through many years of human experience. Large fT′ due to tNM!
In order to enable such processing, it is most important that the photosensitive material always have a constant performance. That is, in the case of the same photosensitive material, the minimum condition is that the quality is exactly the same within the same $1000 production range. Using the light material size (considering from 1!II, the 45th place of the same manufacture is the larger one) I9 cedar (it is even more advantageous because it saves the labor of 4 cupboards, doors, and 7 plates, while n・♀ light The question is how to meet this request from the side of the manufacturer of the material.In order to meet this 91iρen, is it necessary to use the same product 7'?
It is an important technology to make the performance quality even more stable within the tlj level. In famous optical materials, the fluctuations in each of the blue, green, and red I:G optical layers are combined,
This is particularly important because of the 11+T factor and 7...ro factor of color variation. In color photosensitive materials, variations in the red photosensitive layer in particular are often large, and this is an obstacle in constructing a stable color photosensitive material.

When manufacturing photosensitive materials, additives such as binders, surfactants, hardeners, fog suppressants, stabilizers, and couplers are mixed into chemically ripened silver halide grains that are spectrally enhanced by IL [F]. Added to tin halide photographic emulsion coating solution (,
There is a step in which a liquid (referred to as L'J base coating liquid) is prepared. It is well known that this coating solution is coated onto a support and dried to produce a photosensitive material.

After emulsifying, physically ripening, weak salting, and chemically ripening the silver halide copying 2'f emulsion, each of the above additives is continuously prepared and applied without storing the set or pre-coating over time. The bulk method is considered to be the ideal method for producing 1.
,・Complexity of injection control equipment and continuous 7
1: If an abnormality occurs in the large control, the coating solution may not be truncated unless it is allowed to age while the design quality is checked to determine whether coating is allowed. If the above-mentioned abnormality is discovered after coating, there is a risk that it will result in a huge loss.

For kneading, there is an advantage that abnormalities can be detected before PT cloth is applied by storing the set in each process or inspecting the coating solution over time (during the test).Furthermore, the equipment can perform batch processing, so there is no need to worry about packaging. It is also possible to prevent and simplify the process.

In this case, the coating solution described above is coated at a constant temperature for several to several tens of hours after preparation, but the quality of the finished photosensitive material must remain constant during this time. −(
No. However, the present situation is that coating solutions containing spectrally sensitized halogenated ζ]4 copying emulsions cause hc4 degree fluctuations, gradation fluctuations, capri increases, etc. over time, and improvements have not yet been made.

In order to prevent changes in performance during storage of this coating solution, especially changes in sensitivity, for example, a method of adding azoles or azaindene compounds known as stabilizers, or a method of adding a preservative such as hydroquinone or sulfine RD t'le. ,
Alternatively, a method has been proposed in which a certain copolymer and an active whitening agent are used in combination, as described in JP-A-49-111629, but these techniques can also be sufficiently effective. isn't it.

Therefore, the first object of the present invention is to provide a stable coating liquid with extremely small fluctuations in performance over a long period of time. A second object of the present invention is to provide a photosensitive material 11 that always has constant quality.
The goal is to provide the following.

The object is to provide a method for producing a silver halide button photographic emulsion in which at least two sensitizing dyes having different chemical structures are added to a silver halide V true emulsion.
Surface dyes are applied during the chemical ripening of the 1-chemical ripening of the non-logenated chain copy emulsion and during the chemical ripening before coating on the support.
j, and added in said 1-chemical ripening-1/
S 1.1 Chemical structure of sensitizing dyes added to silver genide emulsions and chemical structure of sensitizing dyes added before coating on the chemical ripening medium It has been found that a halogenated photographic emulsion can be produced by the fii'J manufacturing method, which is characterized in that the C construction differs by at least t i++ by at least t i++.

At least two sensitizing dyes with different chemical structures are used in this sensitizing process, and are divided into several times during ``chemical ripening'' and ``during chemical ripening and before being coated on the support''. The chemical structure of the sensitizing dye added to the silver halide photographic emulsion differs by at least one type from that of the sensitizing dye added during "chemical ripening in the clear night to before the η2 cloth is rolled onto the support". There are characteristics in adding each sensitizing dye, preferably,
For example, a sensitizing dye a added to a silver halide true emulsion "during chemical ripening" and a sensitizing dye having a different chemical composition from this sensitizing dye a to the sensitizing dye q [chemical ripening time ~ support f4=: There is a method of sensitizing the dye by adding it to the silver halide 7-page emulsion sensitized with the sensitizing dye a during the upper coating.

In addition, the sensitizing dyes added during chemical ripening and the sensitizing dyes added during chemical ripening to coating on a support are each sensitizing dyes with at least one type of different phi-chemical structure. At least two sensitizing dyes of different chemical compositions according to the present invention preferably have a dye. The chemical pattern is different from that of the sensitizing dye that is further added during the period from clear day to before coating on the support. It is preferable that the sensitizing dye added to the silver halide photographic emulsion in [2] is at least one of the compounds represented by the following general formulas (■) and (IT).

However, Y represents sulfur, selenium, or oxygen atom, and Y2
represents a sulfur, yellow or selenium atom, and Zl and Z2 are respectively necessary to form thiazole, oxisazole, benzthiazole, benzselenacyl, benzselenazole, leaftozaazole, naphthoselenazole, or naphthoxazole M. represents an atomic group, and the ring may be replaced by ■rt, and when (lls, n, a form a ring, Z2
Z3 represents a group of atoms necessary to form benzthiazole, benzselenazole, naphthothiazole, or (J naphthoselenazole), and the ring may be modified (R6 , R6 represents a hydration atom, lower alkyl, Jj; or a lower alkoxy group, and R2, R6 and R6ζJ each represent a [( The alkyl group of where e is 0 or I, and when the compound forms an inner salt, l is O
It is.

Such compounds used in the present invention are disclosed in Japanese Unexamined Patent Application Publication No. 1986-
5035, UK special i! + No. 489.335, same No. 1
It can be synthesized by the method described in No. 096, 877 Mei A11; 1, etc., or according to the merging method described therein.

Examples of sensitizing dyes used in the present invention are shown below, but the compounds used in the present invention are not limited thereto.

I C2TI, (cIT,,)3SO,○11 C2TT5 (C)T2)sSO,.

1 (CH2)2 C2H5 ■ 0CI-T, CI” ]1 C21,
((','1-I2)I SO
3゜1 ((old t)20cTI g
(C112)4:3030 The color sensitive wavelength range of the silver halide 4-page emulsion sensitized by the large cost of sensitization used in the production method according to the present invention is the so-called red-sensitive color light-sensitive material. A preferable effect is achieved when the wavelength range is sensitized.

That is, it is preferable that the sensitizing dye used is a sensitizing dye that imparts color sensitivity to the red-sensitive wavelength region of the true silver halide emulsion.

Coating solution used in the present invention + = "Chemical ripening on a clear night - before coating on the support body" Added red trB The sensitizing dye used to determine the color property is the red 1/1 used during chemical ripening. The amount of sensitization to be applied can be easily determined experimentally.

Furthermore, the sensitizing dye that imparts red sensitivity to be used during the chemical ripening of the present invention is not particularly limited, and may be one that provides the desired color sensitivity wavelength range after spectral sensitivity. It does not support the use of one type Nuze in combination with Sowai-F2.In addition, the sensitized color Nuze added in "Chemical ripening 115-?J ~ before printing on the support" also has no effect on Ichiwa or its use. There is no problem in using the above in combination.

To add these sensitizing dyes to a hydrophilic colloid containing silver halide grains, add water, methanol, ethanol, and fluorine miscible with water. Alcohol, ], 4-butanediol, dimethylformamide, di-so-kirin, benzene, ri-coroborum,
Pyridine, ligroin, acetone, triethylene glycol monomethyl ether, triethanolamine, methyl cellosolve, ethyl cellosolve, phenyl cellosolve~j It is advisable to add it after dissolving it in the Ti Pf solvent.
Each can be used alone or 2 Y:tr J
J may be used in combination.

In the present invention, "during chemical ripening" means adding a sensitizer such as metal base, hypo, thioethers, etc., adding a mercapto compound or an azaindene compound after a certain temperature Iη, and adding a mercapto compound or an azaindene compound. This refers to the process until the humidity is lowered below that level.

[Chemical ripening in the clear night ~ Before application to support finish-1 is Mij.After chemical ripening, binder, surfactant, hardener,
Aiming at the step of adding F11i additives such as fog suppressants, stabilizers, couplers, etc., that is, the step in which the spectrally sensitized silver halide emulsion is about to be coated on the support -L-. .

The silver halide emulsion used in the present invention is a silver halide emulsion containing silver chloride, silver bromide, and silver iodide.
It is possible to apply silver chloride, silver chloride, silver chloride 6). The generation, dispersion and production of these silver halide grains are produced under normal process conditions, including forward mixing θ3, back mixing method, double jet method and their combined methods. Ammonia method or partial ammonia? , l'', alkaline method, neutral method, acidic method, and their combined methods, as well as functional addition method, halogen exchange method, homogeneous precipitation method, etc. are applicable.In particular, monodisperse method obtained by functional addition method can be applied. The present invention cannot be effectively used for silver halide powder of
The average diameter of lJ4 particles is not particularly limited, but is 0.01μ.
~3μ is preferred, or separately formed 2 ilt
, L) l-f- silver halide emulsions may be mixed.

The silver halide emulsion used in the present invention can be chemically sensitized by conventional methods and conditions.

Namely, the gold sensitization method using total complex salts, the reduction sensitization method using reducing substances, the reaction with silver ylene, the compound method containing sulfur, the yellow sensitization method using so-called activated gelatin, and the periodic table ■ [It is possible to use an increase method using the 1st bar of the base 8 that yields to the family Z, etc.

The silver halide emulsion obtained as described in the notes contains li't41c! during the storage of the light-sensitive material or during the development process. However, in order to prevent the formation of fog and fog, various compounds can be added.

These compounds are 4-hydroxy-6-methyl-1,
Many double purple compounds, mercapto compounds, metal IAs, and the like are known, including 3,3a,7-titraazaindene, 3-methylbenzothiazole, and l-7enyl-5-mercaptotetrazole.

In the present invention, it is advantageous to use gelatin as the binder or protective colloid for the silver halide emulsion, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, cellulose derivatives such as didroxyethyl cellulose, carboxymethyl cellulose, cellulose esters, polyvinyl alcohol,
Polyvinyl alcohol f11! minute acetal, poly-
A wide variety of synthetic aqueous polymeric materials can be used, such as mono- or copolymers of N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and the like.

In addition, the silver halide photographic emulsion coating i'+'j of the present invention may contain known conventional accelerators, surfactants, antifoaming agents, antistatic agents, hardeners, film property improvers, and anti-staining agents. , a sharpness improver, a mordant, a brightener, and other additives.

The silver halide true emulsion of the present invention generally has 1. A silver halide photosensitive material is produced by coating and drying it on a suitable support.The supports used at this time include glass, cellulose acetate, cellulose acetate, polyester, polyamide, and polyester. A support such as a silver halide or a laminate of two or more substrates, such as a laminate of a string and a polyolefin (polyethylene, polypropylene, etc.), is used. Surface modification treatments are commonly used to improve adhesion to emulsions, such as electronic
Those that have been subjected to surface treatment such as bombardment treatment or subbing treatment to provide a subbing layer are used.

The silver halide 7-grain emulsion is coated on this support and dried by a commonly known coating method such as dip coating, roller coating, bead coating, curtain flow coating, etc., and then dried.

The present invention applies to general silver halide color VVt photosensitive materials, for reversal processing, for tLI contact and reversal, for diffusion transfer 7r,
Not only can it be applied to color photosensitive materials such as those for color bleaching, but also when the coupler develops a black color or is a so-called colorless coupler, it can be used as a general purpose silver halide black and white photosensitive material. , for X-rays, for printing, M cavity, ■
It can be applied to photosensitive materials ranging from those used for recording sub-rays. The present invention is effective when used with color photographic paper that changes the color balance.

Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example-■ Simultaneous emulsification mixing by 7F8 method, aging bales at 50°C for 40 minutes, desalting by normal precipitation water washing V; particle size (1341
Chlorobromide of t (J! Emulsion (equalization plane 28 mol%, bromide ε7.
! 72 mol%) was obtained. To this emulsion, 3 m of hypo and 50 m of azotrines were added and chemically ripened at 55°C for 80 minutes.1. +
, I did it and stored it in a cooling set. In addition, another emulsion was prepared in a similar manner to which the sensitizing dyes listed in Table 1 were added 10 minutes after adding adenine at 55°C.

Furthermore, the emulsion of the chemical ripening method is dissolved, and the increase f1 added before coating is
13 dyes were added as shown in Table 1, and further 0.2 g of 4-nitroxy-6-methyl-' + 3+ 38z 7-titrazaindene and 0 2-mercaptobenzthiazole were added.
．． 049, a protect-dispersed coupler dispersion containing cyan coupler (CC-t) was added and moisturized at 42°C. After a certain period of time, a hardener (example compound IT-1) was added.
15 m(j) per 1 g of gelatin (add 0.25 g of surfactant (Exemplified Compound 5-2) per 1 liter of finishing emulsion, and mark on polyethylene laminated paper) is 0.3 gAn
A sample was obtained by coating and drying so that the result was '.

The amounts of the various additives are 1.1 per mole of halogenated 's='A.

Sensitizing dye Human sensitizing dye B 1-1 CI-2-1 Sodium dodecylbenzenesulfonate-2 C2115-CTIT-L2- COO-CI(-SO
3NaC205-C6IL□-COO-CH2 These samples were heated using a 3000'K tungsten light source and a red filter (sharp power,
0■Hoya Glass 8! ! After treatment and drying according to the treatment method shown below, Sakura Color Temporary Liver PT) type A-65 (manufactured by Roku Konishi Teiko Co., Ltd.)
Sensitometric measurements were performed using

Table 1 shows the results regarding changes in red sensitivity. The sensitivity is expressed as relative sensitivity, with the sensitivity of the coating applied after 1 hour being set as ]00.

Treatment process (32.8℃) Processing time Color development
Bleach and fix for 3 minutes, wash with water for 1 minute and 30 seconds, dry for 3 minutes and 30 seconds
Dry color developing solution composition Bleach-fixing solution composition Oxidation-reduction potential -70+nV Table 1 Added sensitizing dyes and their surroundings.

Samples from Al to 4.15.16 in which a sensitizing dye was added either during chemical ripening or before coating (sensitivity decreased significantly with increasing time).

Trial 1, in which the sensitizing dye according to the present invention was added in two parts, had a small change in sensitivity and was modified, but in particular, Adding pigment before coating A 9-14, +7-20.2゛? ~
2-1 has a large improvement in sensitivity change.

Also, when adding the same dye in portions, the Ii 3 degree ratio change is large, and the sensitivity changes when the chemical structure of the sensitizing dyes added during chemical ripening and during chemical ripening to before coating differs! It is clear that j, j, is small. It is clear from samples j626 to j29 that an effect can be seen even when a sensitizing dye is used in combination.

Example-2 Emulsion mixed by ammonia method, emulsion C41') O
c.

1) A silver chloride bromoiodide emulsion with a grain size of 0.42 tt (A silver chloride iodide emulsion with a grain size of 0.42 tt) 5 mol %, silver bromide 94.7 mol %, and silver iodide 0.3 mol %).

To this emulsion were added 0.5 m9 of chloroauric acid, 3 m9 of ammonium thiocyanate, 20 m9 of adenine, and 3 m9 of hypo.
were added sequentially, chemically aged at 50'C for 70 minutes, and then cooled.

I saved it. Add hypo in the same way and then heat to 50℃.
After the addition, the emulsions to which the sensitizing dyes listed in Table 2 were added were separately mixed.

Furthermore, the chemically ripened emulsion was dissolved, and the 4-hydroxy-
6-Methyl-I+ 31” al 7-chitrazaindene 0.3 g, 2-mercaptobenzothiazole o, os
g. Add a protected coupler dispersion containing cyan coupler (CC-1) and moisturize at 40°C.
After a certain period of time, a hardening agent (Exemplary Compound 1-1-2)
2.5 m9 per 1 g of gelatin and a surfactant (exemplified compound S-).1. o, iEl per 1 liter of agent All processed, 1,1 silver on polyethylene laminated paper 0,3
A sample was obtained by coating and drying to give a coating ratio of 5 jj/yrt.

In addition, h4 of each glaze addition cutting is the addition per mole of norogenization Ql, J, )+1.

These samples were subjected to cytometry using the same 41:1 method as in Example 1. The results are not shown in 1Y-2.

It is clear that the change in the emulsion over time is smaller when the addition is 7.

Furthermore, it is clear that even when a mixture of sensitizing dyes added with a lining solution is used, the change in sensitivity is small and the effect is large.

Agent Tsune Kuwa Hara 337-

Claims (1)

[Claims] In a method for producing a silver halide photographic emulsion, in which at least two types of sensitizing dyes having different chemical structures are added to silver halide photographic emulsion 1, the at least two types of sensitizing dyes are The sensitized color is added separately to the emulsion during chemical ripening and after chemical ripening to before coating on the support, and is added to the silver halide photographic emulsion during chemical ripening. halogenation characterized by having at least one chemical structure different from the chemical structure of the sensitizing dye added at the time of chemical ripening to the preparation of the paper onto the support. Method for producing silver photographic emulsion.