JP2729668B2 - Method for producing photographic silver halide emulsion - Google Patents

Description

The present invention relates to a method for producing a photographic silver halide emulsion,
More specifically, the present invention relates to a method for producing a photographic silver halide emulsion in which silver halide crystals are grown in the presence of a specific chemical substance.

[Background of the Invention]

In recent years, demands for high sensitivity and high image quality of silver halide photographic light-sensitive materials have been increasing more and more. In order to respond to such demands, various techniques have been proposed for controlling the crystal shape, size, and the like of silver halide in a photographic silver halide emulsion used for a photosensitive material.

Japanese Patent Application Laid-Open No. 60-122935 discloses that a silver halide emulsion having good monodispersibility is obtained by growing a crystal in the presence of a tetraazaindene compound.

JP-A-60-222842 discloses a method for obtaining a silver halide emulsion containing silver halide grains having a novel crystal plane by growing crystals in the presence of a mercapto compound.

Similarly, JP-A Nos. 62-124552, 62-123446, 62-123
No. 447, No. 62-124550 and No. 62-124551 disclose a method of obtaining a silver halide emulsion containing grains having a new crystal plane by growing a crystal in the presence of a specific compound. It has been disclosed.

However, in the crystal growth control technology represented by the above technology, most of the crystal growth control agents used are compounds having an adsorptivity to a silver halide emulsion, and the compound itself has a desensitizing effect. Or a sensitizing dye, such as a sensitizing dye, has the drawback of impairing the function of a photographic additive having an adsorptivity to the surface of a silver halide emulsion or significantly weakening its effect.

There is also a method in which silver halide grains are grown in the presence of a sensitizing dye. However, this technique has a drawback in that it is not possible to impart favorable spectral sensitizing characteristics due to the color sensitivity of the remaining sensitizing dye. was there.

[Object of the invention]

An object of the present invention is to make it possible to perform desired crystal growth control without impairing photographic characteristics by performing crystal growth in the presence of a specific compound, thereby obtaining, for example, high sensitivity and low fog. It is an object of the present invention to provide a method for producing a silver halide emulsion capable of obtaining an emulsion having

[Configuration of the invention]

It is an object of the present invention that the amino group in the hydrophilic protein molecule is 2,4-bis (O-
Methoxypolyethylene glycol) -S-triazine-
6-yl-substituted hydrophilic protein and a carboxyl group terminal of a hydrophilic protein degradation product in which an amino group is substituted with 2,4-bis (O-methoxypolyethylene glycol) -S-triazin-6-yl; Crystal growth of silver halide in the presence of at least one arbitrarily selected from the group consisting of compounds in which the amino portion of an alanine aliphatic alcohol ester represented by the general formula (I) is amide-bonded. This was achieved by a method for producing a photographic silver halide emulsion characterized by the following.

In the formula, R represents an alkyl group having 2 to 22 carbon atoms, an alkenyl group, or an alkadienyl group.

 Hereinafter, the present invention will be described in detail.

First, in the method for producing a silver halide of the present invention, a compound to be present at the time of crystal growth (hereinafter, also appropriately referred to as “compound of the present invention”) will be described.

Among the compounds constituting the group of compounds of the present invention, hydrophilic proteins in which amino groups in hydrophilic protein molecules have been substituted with 2,4-bis (O-methoxypolyethylene glycol) -S-triazin-6-yl ( Hereinafter, appropriately referred to as “substituted hydrophilic protein of the present invention” can be represented by the following schematic diagram (II).

In the substance shown in the schematic diagram (II), the average molecular weight of the O-methoxypolyethylene glycol moiety is about 200 to 1
4,000 is preferred.

2,4-bis (O-methoxypolyethylene glycol)
The substitution amount of -S-triazin-6-yl is preferably 30 mol% or more based on the total amount of amino groups in the hydrolyzate of the hydrophilic protein.

2,4-bis (O-methoxypolyethylene glycol)
Examples of the hydrophilic protein to be substituted with -S-triazin-6-yl include casein, gelatin, sericin, soluble collagen, zein, serum albumin, lactalbumin, and ovalbumin, and these may be used alone or in combination. it can. Among these proteins, proteins other than sericin are sold as reagents. Also,
Sericin can be obtained by extracting hot water from cut cocoons and freeze-drying. However, it is preferable to use gelatin in view of the hydrophilicity and safety of the protein, the solubility in the reaction system during the oxygen reaction, the reaction efficiency, and the like.

Next, a method for producing the substituted hydrophilic protein of the present invention will be described.

Basically, the following reaction steps can be used.

O-methoxy polyethylene glycol (II-1) and 2,4,
By reacting with 6-trichloro-S-triazine (II-2), 2,4-bis (O-methoxypolyethylene glycol) -6-chloro-S-triazine (II-3) is obtained.
Is manufactured. (Nishimura, H., Takahasi, K., Sakurai,
K., Fujinuma, K., Imamura, Y., Oba, M., Inada, Y., Life Sc
i., 83,1467-1478 (1983) Next, activated with a hydrophilic protein and cyanuric chloride2,
4-bis (O-methoxypolyethylene glycol) -6
-Chloro-S-triazine (II-3) is mixed in a borate buffer and reacted at 37 ° C., so that the amino group in the protein is 2,4-bis (O-methoxypolyethylene glycol) -S-triazine. Those substituted with -6-yl (hereinafter appropriately referred to as polyethylene glycol-modified protein)
(II-4) is obtained. At this time, the modification rate of the polyethylene glycol (that is, the amino group in the protein was 2,4-bis (O-
Methoxypolyethylene glycol) -S-triazine-
The rate of substitution with 6-yl) can be controlled by adjusting conditions such as the reaction time.

Next, a specific production example will be described.

Production Method Example 1 (Synthesis of Polyethylene Glycol-Modified Gelatin) In this production method example, gelatin was used as a hydrophilic protein.

In 150 ml of 0.1 molar borate buffer (pH 9.2), 11 g of gelatin, which is a hydrophilic protein, is dissolved.

On the other hand, 2,4-bis (O-
Methoxypolyethylene glycol) -6-chloro-5-
Triazine (II-3) [trade name activated PEG ₂ (manufactured by Seikagaku Corporation) was used. In this case, 30 g of methoxypolyethylene glycol having a number average molecular weight of 5,000] was dissolved in 150 ml of a 0.1 molar borate buffer (pH 9.2), and mixed with the above gelatin solution. Then, it was immersed in a hot water bath at 37 ° C. and sufficiently stirred to homogenize. After the reaction for 8 hours, 600 ml of a 0.1 molar phosphate buffer (pH 7.0) was added to stop the reaction. At this time, the modification ratio of polyethylene glycol to gelatin was 70 mol% based on the total amount of amino groups in the gelatin molecule as a result of quantification of amino groups using the trinitrobenzenesulfonic acid (TNBS) method.

After stopping the reaction, unreacted activated polyethylene glycol was removed using a filtration membrane having a molecular weight cut off of 50,000. Then, it was placed in a cellophane tube (dialysis tube), dialyzed in running water for two days and nights, and lyophilized to obtain about 36 g of polyethylene glycol-modified gelatin.

Production method-2 By setting the reaction time between activated polyethylene glycol and gelatin to 1 hour, the polyethylene glycol chain 50
% Modified gelatin was obtained. Other reaction conditions are shown in Production Example-1.
Is the same as

Production method-3 Except that the average molecular weight of methoxypolyethylene glycol activated with cyanuric chloride was 2,000, the reaction was carried out under the same conditions as in Production method-1 to obtain a 70% polyethylene glycol (average molecular weight 2,000) modified gelatin. Obtained.

Among the compounds constituting the group of the compounds of the present invention, the amino group is 2,4-bis (O-methoxypolyethylene glycol)
A compound in which a carboxyl group terminal of a hydrolyzate of a hydrophilic protein substituted with -S-triazin-6-yl and an amino moiety of an alanine aliphatic alcohol ester represented by the following general formula (I) are amide-bonded (hereinafter referred to as appropriate) , "The binding compound of the present invention" and the like) are represented by the following schematic diagrams (II
I) can be expressed.

R represents an alkyl group, an alkenyl group, or an alkadienyl group having 2 to 22 carbon atoms.

The average molecular weight of the O-methoxy polyethylene glycol moiety is preferably about 200-14000. 2,4-bis (O-methoxypolyethylene glycol) -S-triazine-6
The substitution amount of yl is preferably 30 mol% or more based on the total amount of amino groups in the hydrolyzate of hydrophilic protein.

The binding compound of the present invention comprises an ester represented by the general formula (I) and a hydrophilic protein in which the amino group is substituted with 2,4-bis (O-methoxypolyethylene glycol) -S-triazin-6-yl, namely the present invention. The binding compound (III) of the present invention can be obtained by reacting the substituted hydrophilic protein of the present invention with the substituted hydrophilic protein. It can be said that the ester of the above was used. For the substituted hydrophilic protein of the present invention, those obtained by reacting amino acids other than alanine, for example, those using glycine, tyrosine, tryptophan, etc., have poor solubility at the time of esterification and the reaction yield is low. There is a problem of low. In addition, when an amino acid having a β side chain such as valine, leucine or isoleucine, or a basic amino acid such as lysine, arginine or histidine, or a dibasic acid such as aspartic acid or glutamic acid is used, an oxygen reaction, that is, Only an amino acid ester having poor solubility in the reaction with the hydrophilic protein in the presence of the peptidase is obtained, resulting in a poor reaction yield and unreacted impurities.

In contrast, the binding compound of the present invention, which can be obtained by using alanine as an amino acid constituting an ester, has extremely high solubility in the esterification step and the synthesis step of the protein-based emulsifier in the oxygen reaction, and any other The reaction yield is higher than when amino acids are used.

Examples of the alcohol for constituting the aliphatic organic group of the alanine aliphatic alcohol ester represented by the general formula (I) include those having 2 to 13 carbon atoms, such as ethanol, propanol, butanol, heptanol, hexanol, octanol, decanol, and the like. Dodecanol can be cited, myristyl alcohol having 14 to 22 carbon atoms,
Examples thereof include pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, aralkyl alcohol, and behenyl alcohol.
Also, 2-pentenol-1, 11-dodecenol-1,
Unsaturated alcohols such as oleyl alcohol may also be mentioned. In the case of unsaturated alcohols, the trans form is preferable to the cis form, because the reactivity of the oxygen reaction (aminolysis reaction) in the grafting reaction of the hydrophilic protein is higher. Further, there may be mentioned branched alcohols such as isopropyl alcohol, isobutyl alcohol and tert-butyl alcohol. In the case of a branched-chain alcohol, if the bulky structure is used, the reactivity of the oxygen reaction (aminolysis reaction) tends to be deteriorated. Therefore, an alcohol in an iso form is preferable. Among these alcohols, it is particularly preferable to use an alcohol in which the carbon number of the aliphatic organic group (organic group of the aliphatic alcohol) in the alanine aliphatic alcohol ester is in the range of 14 to 22. When an alanine aliphatic alcohol ester having less than 14 carbon atoms in the aliphatic organic group is used, the emulsifying power of the resulting protein-based emulsion tends to be inferior, and the non-emulsified product containing the same has a long-term Storage (for example, storage at 45 ° C. for 6 months) may cause a slight off-flavor. When an alcohol having an aliphatic organic group having more than 22 carbon atoms is used, the solubility of the alanine aliphatic alcohol ester may be deteriorated, and the oxygen reaction (aminolysis reaction) in the graft reaction of the hydrophilic protein tends to decrease. There is. Therefore, it is preferable to use the alcohol such that the carbon number of the aliphatic organic group in the alanine aliphatic alcohol ester falls within the range of 14 to 22. There are two types of alanine, L-type and D-type, and it is preferable to use L-type from the viewpoint of the yield of the protein-based emulsifier.

The binding compound of the present invention can be produced, for example, as follows. First, an alanine aliphatic alcohol ester is prepared as a hydrophilic protein grafting agent. For this purpose, using alanine and aliphatic alcohols as raw materials,
A known esterification reaction is appropriately selected and applied. Thereby, an alanine aliphatic alcohol ester can be produced. However, according to the method described below in which a free alanine aliphatic alcohol ester is passed through p-toluenesulfonic acid, more excellent results can be obtained.

That is, alanine and an aliphatic alcohol are reacted in the presence of p-toluenesulfonic acid as a Bronsted acid catalyst,
A p-toluenesulfonic acid salt of an alanine aliphatic ester is obtained. Then, the alanine aliphatic alcohol ester-p-toluenesulfonic acid is brought into contact with an alkaline medium to remove p-toluenesulfonic acid.

It is preferable to use a sodium hydroxide or potassium hydroxide solution as the alkaline medium. The alkali concentration is preferably from 0.01 to 5N, more preferably from 0.05 to 2N. The alkali treatment is preferably performed by salting out in the presence of salts.

Salts for salting out include alkali metal salts and ammonium salts, and specific examples include sodium chloride, potassium chloride, potassium carbonate, potassium phosphate, ammonium sulfate, and sodium sulfate. Sodium chloride and potassium chloride are preferred. The salt concentration for salting out is usually
The range is preferably 0.5% to 25%, more preferably 1% to 1%.
0%.

The alanine aliphatic alcohol ester-p-toluenesulfonate is a solid, but the free alanine aliphatic alcohol ester thus obtained is in the form of an oil or a solid having a low melting point. In the reaction with a soluble protein, the compound has extremely good solubility in a buffer solution-acetone mixture used as a reaction system solvent and can react in a homogeneous system.

As described above, p-toluenesulfonic acid may not be released from alanine aliphatic alcohol ester-p-toluenesulfonic acid salt, and may be used in the form of a salt. Alanine aliphatic alcohol ester exhibits excellent solubility even in the form of p-toluenesulfonate, so that unlike other amino acid esters, it can be used as p-toluenesulfonate That's it. Therefore,
In the alanine aliphatic alcohol ester referred to in the present invention,
Both those from which p-toluenesulfonic acid is eliminated and those from which p-toluenesulfonic acid is not eliminated are included. Residues such as unreacted alanine and p-toluenesulfonic acid in the production system can be effectively removed, and the target product can be obtained in a highly purified state.

Next, the obtained alanine aliphatic alcohol ester is reacted with a hydrophilic protein in the presence of endopeptidase. Endopeptidase used in an enzymatic reaction has an action of cleaving a protein from its central part.
This includes serine proteases, thiol proteases, carboxyl proteases, metalloproteases, and other endopeptidases. Of these,
Most preferably, a thiol protease is used. Examples of the thiol protease include papain, chymopapain, promelain, ficin, cucumber fruit protease, cathepsin B, L, S, yeast protease B or TZ-peptidase. These may be used alone or in combination. When alanine aliphatic alcohol ester is reacted with a hydrophilic protein in the presence of endopeptidase, the hydrophilic protein is cleaved from the center by the action of endopeptidase and decomposed,
At the same time, the amino portion of the alanine aliphatic alcohol ester is amide-bonded to the carboxy terminus of the resulting decomposed product, thereby obtaining the desired protein emulsifier.

Next, a specific method for producing the compound represented by the formula (III) will be described.

The hydrophilic protein in which the amino group is substituted with 2,4-bis (O-methoxypolyethylene glycol) -S-triazin-6-yl can be prepared in the same manner as in the above-described method for producing the substituted hydrophilic protein of the present invention. -Methoxypolyethylene glycol (II-1) and 2,4,6-trichloro-S-triazine (I
I-2) to give 2,4-bis (O-methoxypolyethylene glycol) -6-chloro-S-triazine (II-3), which was activated with a hydrophilic protein and cyanuric chloride. This (II-3) is mixed with borate buffer,
It can be obtained by reacting at 37 ° C.

On the other hand, the alanine aliphatic ester (III-1) can be obtained by subjecting alanine and an alcohol to ester bonding in an organic solvent such as benzene using p-toluenesulfonic acid or the like as a catalyst and heating to reflux (Japanese Patent Application Laid-Open (JP-A) No. 2000-150630). No. 60-94124).

Next, a hydrophilic protein (II) modified with alanine aliphatic ester (III-1) and methoxypolyethylene glycol
-4) in the presence of endopeptidase to give a binding compound of the present invention represented by the formula (III) (polyethylene glycol-modified protein-based emulsifier) (II
I) can be obtained.

(III-1) + (II-4) → (III) Specifically, an alanine aliphatic ester and a hydrophilic protein modified with polyethylene glycol are added to papain or the like in ethanol or carbonate buffer. At 37 ° C. When reacting the protein with the amino acid long-chain alkyl ester, if a compound having a thiol group such as 2-mercaptoethanol, cysteine, dithiothreitol, glutathione, or dimercaprol is added as an activator, the reaction is further facilitated. .

 Next, a specific example of the manufacturing method will be described.

Production method-4 (Synthesis of polyethylene glycol-modified protein-based emulsifier) First, in the same manner as in Production method-1, about 36 g of polyethylene glycol-modified gelatin was obtained.

Next, 2 g of the polyethylene glycol-modified gelatin solution obtained as described above was added to 45 ml of a 20% ethanol solution.
A molar sodium carbonate solution was added to adjust the solution pH to 9.1. To this, L-alanyl myristyl ester was added.
2.88 ml was added, thoroughly stirred, and homogenized. Next, 0.078 g of L-cysteine hydrochloride was added thereto, and 0.09 g of papain, which is an endopeptidase, was further added. The mixture was reacted with stirring for 8 hours. To stop the reaction, add concentrated hydrochloric acid and add solution pH.
Was set to 2.0. It was dialyzed and then lyophilized. This is further suspended in 800 ml of benzene. The suspension is filtered and acetone is added to the filtrate until no precipitation occurs, and the precipitate is collected. Next, the precipitate was washed with acetone and diethyl ether, and the solvent was removed to obtain about 7 g of a polyethylene glycol-modified protein-based emulsifier.

Production Method-5 In the synthesis of polyethylene glycol-modified gelatin, the reaction was carried out under the same conditions as in Production Example-4 except that 50% of the amino groups in the gelatin were modified with polyethylene glycol, and a 50% polyethylene glycol-modified protein-based emulsifier was used. I got

Production Example-6 A reaction was carried out under the same conditions as in Production Example-4 except that the average molecular weight of methoxypolyethylene glycol activated with cyanuric chloride was 2,000, and a 70% polyethylene glycol (average molecular weight of 2,000) modified protein system was used. An emulsifier was obtained.

Production Example-7 In the synthesis of the polyethylene glycol-modified protein-based emulsifier of Production Example-4, the same conditions as in Production Example-4 were used except that L-alanyllauryl ester was used instead of L-alanylmyristyl ester. This was performed to obtain a 70% polyethylene glycol-modified protein-based emulsifier.

In the present invention, the photographic silver halide emulsion grows the silver halide crystal in the presence of at least one compound of the present invention described above.

In growing crystals, the compound of the present invention can be present at any time. Means for making it exist (addition method and the like) are also optional. Since the compound of the present invention itself can be used as a dispersion medium for forming a hydrophilic protective colloid system, the compound of the present invention is used as a dispersion medium by forming silver halide particles in a hydrophilic colloid system. Can be used. Preferably, a hydrophilic colloid such as gelatin is added so as to coexist with it. The amount of the compound of the present invention is not particularly limited, and may be selected according to each condition. In general, the amount of the compound of the present invention varies somewhat depending on the composition and size of silver halide grains, growth conditions such as pH, etc., but is preferably 10 ^{-5 to} 10 g, more preferably 10 ^-4 , per mol of silver halide. It is preferable to add の 5 × 10 ⁻¹ g.

The conditions for forming silver halide grains are not particularly limited,
Preferred pH values are 1 to 10, particularly preferably 2 to 9,
Preferred pAg value is 5.0 to 12.0, particularly preferably 7.0
~ 11.0, preferred temperature conditions are 30 ~ 90 ° C, particularly preferred
The temperature is 35 to 80 ° C., and it is preferable to form silver halide grains in such a range.

Next, the method for producing a silver halide emulsion of the present invention will be further described as follows.

The present invention can be applied to a method for producing an emulsion having any composition as silver halide. For example, any silver halide composition used in ordinary silver halide emulsions such as silver iodide, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Can be used as a method for producing an emulsion. The present invention is particularly effective when used as a method for producing an emulsion composed of silver iodide, silver iodobromide, and silver chloroiodobromide. A remarkable effect can be obtained by applying the present invention to a method for producing a silver iodobromide emulsion having a concentration of 0.5 to 40 mol%.

In the present invention, silver halide grains may be grown by any of an acidic method, a neutral method, and an ammonia method.
The particles may be grown at a time following the formation,
After the seed particles are formed, they may be grown. The method of producing the seed particles and the method of growing may be the same or different. The compound of the present invention may be present at any time of these nucleation and / or subsequent crystal growth, and when seed particles are formed, the seed particles are used as a seed and / or the seed is used as a seed. It can be at any point during subsequent growth. In addition, desalting may be appropriately performed during the crystal growth.
When the compound of the present invention is present before the desalting, the desalting can be carried out so as to remove the compound of the present invention that was present before. Preferably, in the silver halide emulsion, a halide ion and a silver ion may be mixed at the same time, or the other may be mixed in a liquid in which one is present. At this time, the compound of the present invention may be pre-existing in a liquid containing any of the ions, may be pre-existing in a reaction vessel or the like for performing the reaction, It may be added in the middle as needed to be present.

A silver halide emulsion is formed by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and pAg of a mixed reaction system (in a reaction vessel) while taking into account the critical growth rate of silver halide crystals. You may. By this method, the crystal control effect of the compound of the present invention becomes more effective, and for example, silver halide grains having a regular crystal form and a nearly uniform grain size can be obtained. After the growth, the halogen composition of the grains may be changed using a conversion method.

In the present invention, the silver halide emulsion, during its production, in addition to the compound of the present invention, if necessary, in combination with a silver halide solvent, the grain size of silver halide grains, the shape of the grains, the grain size distribution and The growth rate of the particles can be controlled.

In the present invention, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming and / or growing particles). Containing at least one selected from the group consisting of a complex salt and a metal ion. The metal ion can be added to the inside of the particle and / or the surface of the particle by adding a metal ion. A reduction sensitizing nucleus can be provided inside and / or on the grain surface.

Unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. When removing the salts, a Research Disclosure (hereinafter abbreviated as RD) 1
It can be performed based on the method described in 7643.

The silver halide grains of the silver halide emulsion may have a uniform silver halide composition distribution within the grains, but may have different silver halide compositions between the inside of the grains and the surface layer.
It may be a shell particle. For core / shell particles,
The compounds of the present invention may be present during core growth or shell growth. For example, when producing an internal high iodine type silver iodobromide emulsion, the compound of the present invention can be present when a high mode core is grown.

The present invention can also be applied to the preparation of an emulsion containing tabular grains. In this case, the tabular grains may be core / shell grains.

The silver halide grains of the emulsion obtained by the present invention may be grains whose latent image is mainly formed on the surface or grains whose latent image is mainly formed inside the grains.

According to the present invention, silver halide grains can be controlled to have any crystal form having a regular crystal form such as a cubic, octahedral, or tetradecahedral. Further, it can be controlled to have an irregular crystal form such as a sphere or a plate. Further, in these particles, the ratio between the (100) plane and the (111) plane can be arbitrarily controlled. The grains in the emulsion may have a complex form of the above-mentioned crystal forms, and grains of various crystal forms may be mixed. According to the present invention, appropriate control can be performed so as to obtain a desired shape and crystal form.

The average grain size (the grain size represents the diameter of a circle having an area equal to the projected area) of the silver halide grains in the emulsion obtained according to the present invention is preferably from 0.05 to 5 μm, and particularly preferably from 0.1 to 3 μm. .

According to the invention, the grain size distribution of the silver halide emulsion can be controlled. An emulsion having a wide grain size distribution or an emulsion having a narrow grain size distribution can be obtained. For example, an emulsion having a narrow size distribution can be formed as desired.

In the practice of the present invention, two or more kinds of silver halide emulsions formed separately can be used as a mixture. In that case, the emulsion obtained by the present invention and other emulsions may be mixed and used.

In the present invention, the silver halide emulsion can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination. See RD 17643 (1978) for more information.

In the present invention, the silver halide emulsion can be optically sensitized to a desired wavelength region using a dye known as a sensitizing dye in the photographic industry. The sensitizing dye may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye, or a compound which does not substantially absorb visible light, and which contains a supersensitizer which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. Is also good.

The silver halide emulsion is subjected to chemical ripening for the purpose of preventing fog during the production process, storage, or photographic processing of the photographic light-sensitive material, or for maintaining photographic performance stably, at the end of chemical ripening, and / or After the completion of chemical ripening and before coating the silver halide emulsion, compounds known as antifoggants or stabilizers in the photographic industry can be added. See RD-17643 (1978) for more information.

As the binder (or protective colloid) of the silver halide emulsion, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, single or copolyesters are preferred. A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a coalescence can also be used. About this, RD-17643 (1978)
Is detailed.

The jelly strength of gelatin as a binder for the silver halide emulsion is not limited, but is preferably at least 250 g (measured by a buggy method).

The silver halide emulsion can be chemically sensitized and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion.

When a light-sensitive material is formed using the emulsion obtained in the present invention, the emulsion layer and other hydrophilic colloid layers constituting the light-sensitive material can be hardened, and can be a plasticizer, a water-insoluble or hardly soluble synthetic layer. A polymer dispersion (latex) can be included.

When used as a color photographic material, the emulsion layer
Couplers are used. That is, when the present invention is applied to, for example, a full-color color light-sensitive material, generally a red-sensitive, green-sensitive, blue-sensitive silver halide emulsion layer is provided,
It can be configured so that couplers each producing a desired color are arbitrarily used.

In addition, a development accelerator, a developer, a silver halide solvent, a color tone agent, by coupling with a colored coupler having a color correction effect, a competitive coupler and an oxidized form of a developing agent.
Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

Photosensitive materials include filter layers, antihalation layers,
An auxiliary layer such as an irradiation prevention layer can be provided. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

To the light-sensitive material, a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator can be added.

As a support for constituting the photosensitive material, any material such as paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate and the like can be used.

In order to obtain a dye image from the light-sensitive material, a commonly known color photographic processing can be performed after exposure.

In the present invention, the additives used in the step of producing an emulsion, in addition to those described above, include Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol.
o. 18716 (November 1976), and the relevant locations are summarized in the following table.

Known photographic additives that can be used in the preparation of the photosensitive emulsion in the practice of the present invention are also described in the above two Research Disclosures, and the locations thereof are shown in the following table.

EXAMPLES Examples and comparative examples of the present invention will be described below.
Needless to say, the present invention is not limited by the following embodiments.

Example 1 In this example, using the following A to E solutions,
An emulsion was prepared as described below.

Solution A Potassium bromide 23.80 g Ossein gelatin 40.00 g Make up to 1000 ml with distilled water Solution B Potassium iodide 33.20 g Ossein gelatin 40.00 g Make up to 1000 ml with distilled water.

Solution C 16.99 g of silver nitrate Make up to 1000 ml with distilled water Solution D 0.17 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene Make up to 1000 ml with distilled water.

Solution E Compound I prepared in Preparation Example 1 (see below) 0.17 g Make up to 1000 ml with distilled water.

The average molecular weight of polyethylene glycol is 5.000. The modification rate of polyethylene glycol is 70 mol% based on the total amount of amino groups. Emulsion using solution D (comparative emulsion) and emulsion using solution E (emulsion according to the present invention) ) Was prepared as described below.

To 10 ml of solution A, add solution D or solution E.
After adjusting the pH to 9.0, 190 ml using distilled water
Finished. While adjusting this solution to 60 ° C, 10 ml of solution C
Was added and aging was performed for 20 minutes. Thus, Table-1
As shown in Table 2, an emulsion obtained by changing the amount using the solution D, an emulsion obtained by changing the amount using the solution E, and an emulsion using neither the solution D nor the solution E were prepared. All are silver bromide emulsions. The turbidity of each ripened emulsion was measured using a turbidimeter. Table 1 shows the results.

An emulsion was prepared in the same manner as described above, except that solution B was used instead of solution A, and solution D or solution E was added as shown in Table 2. Thus, a silver iodide emulsion was obtained. The same measurement was performed as described above, and the results obtained for each emulsion are shown in Table 2.

In Tables 1 and 2, the portion surrounded by the thick line is the data of the emulsion obtained by the method according to the present invention.

Tables 1 and 2 show that the compound I used in the present invention also affects the crystal growth, like tetraazaindene known as a crystal growth control agent. It is considered that the effect is larger than that of tetraazaindene and that the effect is more remarkable on silver iodide (Table 1 for silver bromide emulsion and Table 1 for silver iodide emulsion).
2 from comparison of each data).

Comparative Example 1 A silver iodobromide emulsion containing 10 mol% of silver iodide was prepared using the following five kinds of solutions. The seed emulsion used for preparing the emulsion was a cubic silver iodobromide emulsion containing 2 mol% of silver iodide, and the emulsion grains had an average side length of 0.295 μm and a coefficient of variation of 10%.

(Solution A-1) Ossein gelatin 113g Distilled water 8000ml Polyisopropylene-polyethyleneoxy-disuccinic acid sodium salt 10% ethanol aqueous solution 1.13ml 28% ammonia water 83ml Seed emulsion 0.075mol Distilled water to make 11320ml.

(Solution B-1) Ossein gelatin 40g KBr 104.7g KI 16.6g Make up to 2000ml with distilled water.

(Solution C-1) AgNO ₃ 169.9 g Distilled water 260 ml 28% ammonia water 139 ml Make up to 2000 ml with distilled water.

(Solution D-1) 50% KBr aqueous solution pAg adjustment required amount (Solution E-1) 56% acetic acid aqueous solution pH adjustment required amount (Solution F-1) KBr 17g distilled water 60ml at 50 ° C JP-A-57-92523, Minimum time 79.5 without the generation of small particles in the middle by simultaneous mixing method of solution C-1 and solution B-1 to solution A-1 using the mixed stirring liquid shown in No. 57-92524
Addition took minutes. PAg, pH and solution C- during simultaneous mixing
The addition rate of 1 was controlled as shown in Table-3. pAg and
The pH was controlled by changing the flow rates of the solution D-1, the solution E-1 and the solution B-1 by using a variable flow roller tube pump.

Two minutes after the completion of the addition of the solution C-1, the solution F-1 was added.
After one minute, the pH was adjusted to 6.0 with solution E-1.

Then, desalinated water washing is performed according to a conventional method, and ossein gelatin 1
After dispersing in an aqueous solution containing 4.1 g, the total amount is 425 m with distilled water
Prepared as l. This emulsion is called EM-1.

Comparative Example-2 The (solution A-1) and (solution B-1) used in Comparative Example-1 were added to 4-hydroxy-6-methyl-1,3 which is known as a particle size distribution improving and crystal habit controlling agent. , 3a, 7-Tetraazaindene was added in the amounts shown in Table-4. Otherwise by the same method as in Comparative Example 1, EM-2 to EM-5
Were prepared.

Example 2 The compound I was added to (Solution A-1) and (Solution B-1) used in Comparative Example 1 in the amounts shown in Table-5. Otherwise, by the same method as in Comparative Example 1, EM-6 was used.
EM-9 were prepared.

The results of observing the emulsions EM-1 to EM-9 by an electron microscope are shown in Table-6. From Table 6, it can be seen that the addition of compound I can provide the particle size distribution improving effect and the crystal habit control effect as in the case of adding tetraazaindene.

In addition, when compound I is used, the same effect can be realized with a smaller amount of addition than when tetraazaindene is used.

Comparative Example-3 A silver iodobromide emulsion EM-10 having a silver iodobromide shell of 2.6 mol% was prepared using the following five kinds of solutions.

A monodisperse emulsion having an average grain size of 0.27 μm, a coefficient of variation in grain size distribution of 12.3%, and a silver iodide content of 2 mol% was used as a seed emulsion.

(Solution A-2) Ossein gelatin 34.0 g Distilled water 7779 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 20 ml 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 405 mg 28% aqueous ammonia 117.3 ml 56% acetic acid aqueous solution 72 ml seed emulsion 0.303 mol equivalent (solution B-2) ossein gelatin 18.74 g KBr 760.2 g KI 28.4 g 4-hydroxy-6-methyl-1,3,3a, 7 -Tetraazaindene 1.35 g distilled water 1574 ml (solution C-2) AgNO ₃ 1148 g 28% ammonia water 937 ml Make up to 1930 ml with distilled water.

(Solution D-2) 50% KBr aqueous solution pAg adjustment required amount (Solution E-2) 56% acetic acid aqueous solution pH adjustment required amount At 40 ° C, a mixed stirred solution shown in JP-A-57-92523 and JP-A-57-92524 Using solution A-2 to solution C-2 and solution B-2
Was added by the simultaneous mixing method, requiring a minimum time of 56.5 minutes without generation of small particles in the middle. During the simultaneous mixing, the pAg, the pH and the addition rates of the solutions C-2 and B-2 were controlled as shown in Table-7. The control of pAg and pH was performed while changing the flow rates of the solution D-2, the solution E-2, and the solution B-2 using a roller tube pump having a variable flow rate.

Two minutes after the completion of the addition of the solution C-2, the pAg was adjusted to 10.
The pH was adjusted to 4, and after another 2 minutes the pH was adjusted to 6.0 with solution E-2.

Next, desalinated water washing is performed according to a conventional method, and ossein gelatin is used.
After dispersing in an aqueous solution containing 128.1 g, the total amount is
Adjusted to 3000ml.

Example-3 4-hydroxy-6-methyl-1,3,3 contained in (Solution A-2) and (Solution B-2) used in Comparative Example-3 above
Instead of a, 7-tetraazaindene, Compound I was added to solution A
-2 was added to 81 mg and solution B-2 to 270 mg. Otherwise, EM-11 was prepared in the same manner as in Comparative Example-3.

Electron microscopy revealed that EM-10,
EM-11 has an average particle size of 0.80 μm and a variation coefficient of particle size distribution of 1
It was found to be a high single fraction emulsion of 0.2% and 10.5%.

Example-4 Emulsion samples EM-10 and EM-11 produced according to Comparative Example-3 and Example-3 were divided such that the silver halide content was equivalent to 0.35 mol, and ammonium thiocyanate was used for each. , Using sodium thiosulfate and chloroauric acid for chemical sensitization, and as a green-sensitive sensitizing dye, anhydro-5,
5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide, anhydro-5,5'-diphenyl-9-ethyl-3,3'-di-
(3-sulfopropyl) oxacarbocyanine and anhydro-9-ethyl-3,3'-di- (3-sulfopropyl) -5,6,5, ', 6'-dibenzooxacarbocyanine hydroxide, respectively 20 mg each was added, and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 5-phenyl-1-mercaptotetrazole were further added. Next, 1200 ml of a dispersion (M-1) having the following composition, saponin and 1,2-bisvinylsulfonylethane were added, and the mixture was coated on a cellulose triacetate pace support so that the silver amount was 18 mg / dm ² , followed by drying. Thus, a silver halide photographic material sample having a stable coating film was obtained.

The sample using EM-10 was S-1 and the sample using EM-11 was S
-2.

Dispersion (M-1) 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-tert-amylphenoxyacetamide) -benzamide] -5-pyrazolone as a magenta coupler 8 × 10 ^-3 mole per mole of silver halide, DIR
As the compound, 2- (1-phenyl-5-tetrazolylthio) -4-octadecylsuccinimide-1-indanone was used. This was mixed with tricresyl phosphate, one time the weight of the coupler, as a high boiling organic solvent,
Ethyl acetate was further added to the mixture, and the mixture was heated to 60 ° C. and completely dissolved. This solution was treated with alkanol B (registered trademark, alkyl naphthalene sulfonate manufactured by DuPont).
The mixture was mixed with 50 ml of a 10% aqueous solution and 700 ml of a 10% gelatin aqueous solution and dispersed using a colloid mill. After subjecting these samples and comparative samples to white exposure using a KS-1 sensitometer (manufactured by Konica Corporation) based on the JIS method, the following color development processing was performed.

<Processing process> (37.8 ° C) Processing time 1. Color development 3 minutes 15 seconds 2. Bleaching 6 minutes 30 seconds 3. Rinse 3 minutes 15 seconds 4. Fixed 6 minutes 30 seconds 5. Rinse 3 minutes 15 seconds 6. Stabilization 1 minute 30 seconds 7. Drying Color developer composition: 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.8 g Sodium sulfite anhydrous 0.14 g Hydroxyamine 1/2 sulfate 1.98 g sulfuric acid 0.74 g anhydrous potassium carbonate 28.85 g anhydrous potassium sulfite 5.10 g potassium bromide 1.16 g potassium chloride 0.14 g nitrilotriacetic acid trisodium salt (first water salt) 1.20 g potassium hydroxide 1.48 g water To 1

Bleaching solution composition: Ethylene ammonium salt of ethylenediaminetetraacetic acid 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to adjust the pH to 1, and the pH is adjusted to 6.0 using aqueous ammonia.

Fixer composition: Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH 6.0 with acetic acid.

Stabilizing solution composition: Formalin 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1

The sensitometric results thus obtained are shown in Table-9. Here, the sensitivity is represented by the relative value of the reciprocal of the exposure amount giving fog +0.1 (S-1 is set to 100).

From the above results, it can be seen that the sample using the emulsion obtained by the manufacturing method of the present invention has characteristics of high sensitivity and low fog as compared with the sample using the emulsion manufactured by the conventional manufacturing method. .

Examples -5 to 8 In the above-mentioned Examples -1 to 4, instead of using the compound obtained in the above-mentioned Preparation Example 1 as the compound of the present invention, the emulsifier obtained in the above-mentioned Preparation Example -4 was similarly used. Was.
Others were the same as in Examples-1 to 4. as a result,
The same effects as those of Examples -1 to 4 were obtained.

Examples -9 to 12 In the above-mentioned Examples -1 to 4, instead of using the compound obtained in the above-mentioned Production Example 1 as the compound of the present invention, the emulsifier obtained in the above-mentioned Production Example -7 is similarly used. Was.
Others were the same as in Examples-1 to 4. as a result,
The same effects as those of Examples -1 to 4 were obtained.

〔The invention's effect〕

As described above, according to the method for producing a photographic silver halide emulsion of the present invention, desired crystal growth control can be effectively performed by performing crystal growth in the presence of a specific compound. The photographic properties are not impaired. Rather, an emulsion having high sensitivity and low fog characteristics can be obtained by the method of the present invention, which can be said to be a very advantageous production method.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junichiro Hiraoka, Kanagawa Prefecture, Yokohama City Door ▲ Tsuka ▼ Ward, Higashimatano-cho 42-13-13 (72) Inventor Takemoto Hira, Nakagun Ninomiya-cho, Fujimigaoka 3-chome 8-19 ( 72) Inventor Murakami Umeshi 5-16-5 Kotobuki-cho, Odawara-shi, Kanagawa Prefecture (72) Inventor Soichi Arai 38-Nanashima-cho, Kanagawa-ku, Kanagawa-ku, Kanagawa-ken (56) References JP-A-62-231246 (JP) , A) JP-A-1-166603 (JP, A) JP-A-1-3166739 (JP, A)

Claims (1)

(57) [Claims] (1) the amino group in the hydrophilic protein molecule is 2,4-
Bis (O-methoxypolyethyleneglycol) -S-triazin-6-yl-substituted hydrophilic protein and Amino group substituted with 2,4-bis (O-methoxypolyethyleneglycol) -S-triazin-6-yl At least one arbitrarily selected from the group consisting of a compound comprising an amide bond between a carboxyl group terminal of a hydrophilic protein hydrolyzate and an amino moiety of an alanine aliphatic alcohol ester represented by the following general formula (I): A method for producing a photographic silver halide emulsion, comprising growing silver halide crystals in the presence of seeds. In the formula, R represents an alkyl group having 2 to 22 carbon atoms, an alkenyl group, or an alkadienyl group.