JPH11282109A - Preparation of silver halide emulsion grains - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing the silver halide emulsion grains low in fog and superior in sensitivity, graininess and pressure resistance. SOLUTION: The silver halide emulsion grains are prepared by adding silver ions and halogen ions into a dispersion medium solution containing at least a dispersion medium and water, and adding gelatin as a dispersion medium in an amount of 30-100 weight % of the total medium at the time of growing the silver halide, and adding an oxidant, in advance, to oxidize divalent sulfur to reduce its content to 0-40 μmol/g to remove 20-100 mol% of the residual oxidant amount, and adding the geleatin after reducing the divalent sulfur and removing the oxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing silver halide (hereinafter referred to as "AgX") emulsion grains useful in the field of photography.

[0002]

2. Description of the Related Art Conventionally, gelatin has been widely used as a dispersion medium for forming AgX particles. In many cases, gelatin obtained by an alkali treatment method has been used as it is. Modified gelatin, such as phthalated gelatin, mainly utilizes AgX properties near its isoelectric point to make AgX
It has been used for sedimentation, washing and desalting of emulsions. For example, the description in U.S. Pat. No. 2,614,929 can be referred to. On the other hand, it is disclosed that thinner tabular grains are formed by adding an oxidizing agent to gelatin to oxidize methionine in gelatin and using the oxidized gelatin as a dispersion medium for forming tabular grains. For example, the description in JP-A-62-157024 can be referred to. Furthermore, it discloses that gelatin, which defines the relationship between the chemical modification ratio of amino groups and the methionine content, is used as a dispersion medium for forming tabular grains.
For example, the description in JP-A-8-82883 can be referred to. In these cases, it was found that there was a deterioration in the photographic properties which was presumed to be due to the untreated unreacted oxidant added, but there is no description in those documents.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing AgX emulsion grains having a low fog density and excellent sensitivity, granularity and pressure resistance.

[0004]

The object of the present invention has been attained by the following items. (1) A method for producing silver halide emulsion grains by adding silver ions and halide ions to a dispersion medium solution containing at least a dispersion medium and water, wherein at least 30 to 30% of the total weight of the dispersion medium in the growth process of the grain formation. 100% is gelatin, and the divalent sulfur group is oxidized in advance by the addition of an oxidizing agent, and the content of the divalent sulfur group is 0 to 40 μmol / g.
And the remaining amount of unreacted oxidizing agent is 20 to 100
A method for producing silver halide emulsion grains, characterized in that gelatin is added to the solution after mol% is removed.
Other preferred embodiments of the present invention are as follows. (2) the oxidizing agent is a peroxy compound, and the removal is
An alkali agent, a heavy metal having a specific gravity of 4.0 or more, the metal salt, and one or more of the metal oxides are brought into contact with the remaining oxidizing agent to accelerate the decomposition reaction of the oxidizing agent. The method for producing silver halide emulsion grains according to the above (1), wherein

[0005] (3) amino groups of the gelatin have been chemically modified, the relationship of the chemical modification ratio and divalent sulfur group content and wherein it is the region of a ₁ in FIG. 1 (1), wherein Production method of silver halide emulsion grains. (4) 50 to 1 of the total projected area of the silver halide grains
0% is a tabular grain having a thickness of 0.01 to 0.5 μm and an aspect ratio (diameter / thickness) of 1.5 to 500. Production method. (5) 3.0 to 98% of the number of imidazole groups in the gelatin
Is chemically modified. The method for producing silver halide emulsion grains according to the above (1), wherein

Another preferred embodiment of the present invention is as follows. (6) The tabular grains have two or more twin planes parallel to each other, and 25 to 100% of the twin planes are at least water (dispersion medium having a colloidal silicic acid content of 0 to 50% by weight). ) and 0.1 g / l or more, and the dispersion medium solution containing a first adsorbent according (1.0 mg / l) or below (a) Ag ⁺
(1) The method for producing silver halide emulsion grains according to the above (1), wherein the twin planes are formed by adding ions and halogen ions. (a) (1) A compound containing 1 to 10 ⁴ onium bases in one molecule and different from gelatin. (3) Compounds in which an aromatic ring is substituted with 1 to 7 iodine groups and 1 to 7 -OH groups. (4) A compound containing a nitrogen-containing heterocyclic compound, which contains 1 to 5 heterocycles containing 2 or more nitrogen atoms in a 4- to 7-membered ring per molecule. (5) Cyanine dyes.

(7) Assuming that the chemical modification rate of amino groups of the gelatin before the start of the grain formation is b ₄ , the chemical modification rate b _{5 of the} gelatin at the start of coating of the silver halide grains.
Manufacturing method (3) The silver halide emulsion grains according but which is a 0.8b ₄ ~0.0. (8) When a chemical modification ratio of the imidazole group of the gelatin prior to particle formation start was b _6, the chemical modification ratio b ₇ of the gelatin at the time of application of the silver halide grains 0.8b
_The method for producing silver halide emulsion grains according to the above (6), wherein the number is from _{6 to} 0.0.

[0008]

Next, the present invention will be described in more detail. (I-1) Gelatin oxidation. In a method for producing silver halide emulsion grains by adding silver ions and halide ions to a dispersion medium solution containing at least a dispersion medium and water, 30 to 100% of the total weight of the dispersion medium,
Preferably 60 to 100%, more preferably 90 to 10
0% is gelatin, and the divalent sulfur group is oxidized in advance by the addition of an oxidizing agent, and the content of the divalent sulfur group (μmol /
g) is reduced to 0 to 40, preferably 0 to 15, more preferably 0 to 5, and the remaining unreacted oxidant amount of 20 to
Gelatin added to the solution after 100 mol%, preferably 50-100 mol%, more preferably 90-100 mol% has been removed. Gelatin is a kind of derived protein obtained by converting collagen, which is a hard protein that forms animal connective tissue, into water-soluble by treatment, and is classified into alkali-treated gelatin and acid-treated gelatin depending on the treatment method.
In addition, empt from cations and anions removed from gelatin
y gelatin, gelatin with acid, alkali, hydrolase,
The molecular weight reduced to 10 by any of the heat treatments is 10
Low molecular weight gelatin of 00 to 8 × 10 ⁴ , high molecular weight gelatin of 10 ⁵ to 10 ⁶ in which gelatin molecules are crosslinked with a hardener, amino group, imidazole group, hydroxyl group or carboxyl group of gelatin is chemically modified Modified gelatin,
Gelatin in which 0-100% of the arginine group is ornithinated, and fractionated gelatin in which the molecular weight distribution is controlled can be mentioned. There is no particular limitation on the gelatin source, and any animal connective tissue can be used.
Fish and bone are preferred, and alkali-treated beef bone gelatin is more preferred. The molecular weight distribution is preferably 0.01 to 0.6, more preferably 0.02 to 0.40, and more preferably 0.02 to 0.4 as a coefficient of variation (standard deviation of weight molecular weight distribution / weight average molecular weight).
~ 0.20 is more preferred. Examples of the gelatin having a narrow distribution include fractionated gelatin obtained by ultrafiltration,
The description in the Journal of the Photographic Society of Japan, Vol. 60, pp. 19-27 (1997) can be referred to.

A dispersion medium other than gelatin has a molecular weight of 30.
00-10 known water-soluble organic polymer compound ⁶ (natural polymer and synthetic polymer) can be exemplified. For details of known water-soluble dispersion media and gelatin, and details of chemically modified gelatin, see JP-A-8-82883 and JP-A-8-82883.
-311428, Journal of the Photographic Society of Japan, Vol. 58, 25-
30 (1995), Niwa and Gelatin, Chapter 4, Japan Niwa and Gelatin Industry Association (1987), The Science and Te
chnology of Gelatin, Chapter 7, Academic Press (1977
), Shinsei Chemistry Laboratory Course 1, Protein IV, Tokyo Kagaku Dojin (1991), Applications and Markets of Water-Soluble Polymers, CMC (1984), Water-Soluble Polymers, Chemical Industry Company (1990 Edition), Research Disclosure Magazine, No. 389, item 389
57 (September 1996) (hereinafter referred to as "RD 1996"),
Kazutaka Tanizawa et al., Chemical Modification of Proteins, Hirokawa Shoten (1991
Year) can be referred to. The colloidal silicic acid content (% by weight) of the dispersion medium in the dispersion medium solution during the formation of the twin plane and during the formation of the AgX particles is 0 to 50, preferably 0 to 50.
10, more preferably 0%. The gelatin concentration (g
/ Liter) is preferably 0.01 to 100, and 0.1 to 50
Is more preferred.

In the oxidation, an oxidizing agent is added to a solution containing at least protein and water, mixed, and the temperature, pH,
It can be carried out by adjusting the reaction time. The pH during the oxidation and during the removal is preferably 1 to 12, and the temperature is preferably 5 to 95C, more preferably 20 to 80C.
The concentration (mol / liter) of the oxidizing agent to be added is preferably from 10 ^{-6 to} 1.0, more preferably from 10 ^-5 to 10 ^-1 . The oxidation reaction time and the removal reaction time are preferably 1 minute to 100 hours, more preferably 0.3 to 100 hours, and 1.0 to 3 hours.
0 hours is more preferred. After the oxidizing agent is added and uniformly mixed, the stirring may be continued as it is, but it is more preferable to store the mixture in a constant temperature bath. Molar ratio of residual oxidant after completion of the reaction (mol of residual oxidant / mol of oxidant added) =
b ₁ is preferably 0.01 to 0.8, 0.1 to 0.5 is more preferable. Most preferred combinations of the pH, temperature, reaction time, concentration, and type of oxidizing agent can be used. At the time of the oxidation, the pH is preferably lower, preferably from 1 to 9, more preferably from 2 to 7. Types of oxidizing agents that can be used are described in (I-3). An embodiment in which a weak oxidizing agent is used in a larger amount than the oxidation equivalent and the oxidation is performed over a long period of time is more preferable. This is because the selectivity of the oxidation reaction of the divalent sulfur group is further increased.

Specific examples of the divalent sulfur group include a methionine group, a cysteine group and a cystine group.
The divalent sulfur group is oxidized into a sulfoxide group, a sulfone group, or a sulfonate group. [Sulfoxide groups / (sulfoxide radix + sulfone groups)] = b ₂ is 0-1.0
Can be taken, but 0.3 to 1.0 is particularly preferable.
0.6 to 1.0 is more preferable. Greater the oxidizing power of the oxidizing agent is increased, the value of b ₂ is reduced. This is because the content of cysteine and cystine in gelatin is low (the content of divalent sulfur groups in gelatin ≒ the content of methionine).

(I-2) Method for Removing Residual Oxidant As a method for removing the residual oxidant, the following method can be mentioned. (A1) A reducing agent is added and reacted with the remaining oxidizing agent to invalidate (neutralize) the remaining oxidizing agent. It is preferable to select the type and the amount of the reducing agent optimally by the trial and error method. Preferably, the amount of the reducing agent is determined by using a redox titration method or a redox-designating agent. This is a method in which a reducing agent is added while measuring the oxidation-reduction potential of a solution, and the addition amount is determined so that the potential when the reaction reaches equilibrium is within a certain range. An oxidizing agent is quickly added to the protein solution, and the relationship between the added amount and the potential is determined. At this time, it is preferable that 70 to 100%, preferably 90 to 100%, of the added oxidizing agent is in an unreacted state and that the potential is close to equilibrium. For that purpose, the reaction of the oxidizing agent may be slowed down, and the temperature is usually lowered (preferably 1 to 50 ° C, more preferably 5 to 40 ° C).
do it. The residual oxidant concentration can be known from the potential.

Next, the reducing agent may be gradually added, and the equilibrium potential may be adjusted so as to be a potential within the range satisfying the requirement for the amount of the remaining oxidizing agent. In this case, it is preferable to measure the potential after the added reducing agent sufficiently reacts with the remaining oxidizing agent to reach a reaction equilibrium. For that purpose, the reaction may be accelerated,
Usually, the temperature may be raised (preferably 20 to 90 ° C, more preferably 40 to 80 ° C).

An oxidation-reduction indicator refers to a substance in which the color of an oxidized product and the color of a reduced product are different, and the color is rapidly changed at a certain oxidation-reduction potential. A reducing agent is added in a state where this substance is added, and an addition amount necessary for adjusting the potential to satisfy the above requirements is obtained. In the case of practical use, the reducing agent may be added in the above-described amount without the indicator and allowed to react, and then used as the dispersion medium. (A2) One or more metal catalysts for decomposing the oxidizing agent are added to decompose and deactivate the oxidizing agent. For example, when the oxidizing agent is H ₂ O ₂ , the decomposition reaction of (2H ₂ O ₂ → H ₂ O + O ₂ ) is performed by adding a heavy metal having a specific gravity of 4.0 or more, the metal salt, and the metal oxide. Promotes and removes H ₂ O ₂ .

Specific examples include colloids of a transition metal of Group VIII such as Pt and Pd and Mn metals, metal oxides such as MnO ₂ , Co ₂ O ₃ and PbO ₂ , and salts of iron and copper. In these cases,
The pH of the solution can be selected from 1 to 12, but a higher pH value is preferable because the reaction is accelerated. Therefore pH 4
To 12 are preferable, and pH 6 to 11 is more preferable.

After the decomposition, the metal catalyst is preferably removed from the protein solution. The following method can be mentioned as a removing method. (1) Stop stirring, allow to stand, and gently suck out the supernatant after the catalyst has precipitated. (2) The solution is filtered with a filter, and the catalyst is separated by filtration. (3) The solution is centrifuged to precipitate the catalyst, and the supernatant is gently drawn off. (4) dispersing the catalyst in an aqueous gelatin solution,
A hardener is added and coated on a support. After drying and allowing the hardening reaction to proceed, it is placed in the solution to accelerate the reaction and then removed to achieve the purpose. The hardening prevents the gelatin film from dissolving in the solution. The dry film thickness (μm) is preferably from 0.1 to 100, more preferably from 1 to 30. (5) The catalyst is put into the solution in a non-powder form (for example, a bar, a thin line, a mesh, a particle having a diameter of 3 μm or more, preferably 10 μm to 1 cm) to accelerate the reaction. Remove from solution when no longer needed. (6) A column containing the catalyst is formed, and the solution is passed through the column to achieve the object. The residual amount ratio b ₃ (remaining weight / addition amount) of the catalyst is preferably 0 to 0.4, more preferably 0 to 0.1, and still more preferably 0 to 0.01.

(A3) Addition of a base. The addition of the base accelerates the decomposition reaction of the oxidizing agent. Examples of bases include large positive metal hydroxides (eg, alkali metal and alkaline earth metal hydroxides), amines, and certain metal complexes [eg, Pt (NH ₃ ) ₆ (OH) ₄ ]. Can be mentioned. If the reaction is complete, adding an acid, neutralizing the base ^{_{(H 3 O + + OH -}} →
2H ₂ O). This assumes that the added base has been removed. By reading the increase in pH value due to the addition of the base and the decrease in pH value due to the addition of the acid, the amount of neutralization can be known. After the residual oxidizing agent is removed in this way, it can be added to the AgX particle forming reaction vessel as it is, after dehydration, or after drying. Alternatively, it can be added after cooling, gelling, drying and solidifying. Alternatively, it can be used after deionization with an ion exchange resin.

(A4) Addition of peroxidase When the residual oxidizing agent is H ₂ O ₂ or an organic peroxy compound, the oxidizing agent can be decomposed by adding peroxidase. Peroxidase is generally (H ₂ O ₂ + AH ₂ →
It is a general term for enzymes that catalyze the reaction of 2H ₂ O + A), and is widely distributed in the animal, plant, and microbial communities. Catalase
AH ₂ = H ₂ O ₂ , and examples of AH ₂ being phenols, aromatic amines, cytochrome C, HI, and glutathione can be given. The addition of AH ₂ promotes the decomposition of H ₂ O ₂ . Once the peroxidase is added to the solution, it is difficult to remove it later. In this regard, the methods described in (A1) to (A3) are more preferable.

(I-3) Oxidizing agents, reducing agents, acids and bases. The oxidizing agent, reducing agent, acid and base that can be used in the present invention are as follows. (Oxidizing agent) Specific examples of the oxidizing agent include O ₂ , O ₃ , compounds which easily release oxygen (eg, H ₂ O ₂ , organic thiosulfone compounds, AgO, Ag ₂ O, etc.), peroxides [in the molecule] Oxygen bridge (-O-
O-). Therefore all hydrogen peroxide H-
It can be considered as a derivative of OOH. Depending on the type of the group that substitutes for H, it is classified into inorganic peroxides (classified as metal peroxides and non-metallic peroxides) and organic peroxides.
The more positive the metal peroxide, the more stable the metal. For example, in alkaline earth metals (Ba>Sr>Ca> Mg), examples of metal peroxides include Na ₂ O ₂ , BaO ₂ , MgO ₂ and CaO ₂ , and examples of non-metallic peroxides include KNO ₄ and K ₂ CO ₄ as an organic peroxide example, peroxyformic acid, peroxyacetic acid, peroxybenzoic acid,
Peroxyphthalic acid can be mentioned. The oxidizing power of the peroxide is due to the oxygen of the oxygen bridge. Peroxides typically generate H ₂ O ₂ in acidic aqueous solutions. Peroxyacid salts are also peroxides.

The peroxyacid is an acid having the oxygen bridge, and most of the peroxyacids corresponding to generally known oxygen acids are known. For example _{H 2 SO 5, H 3 PO} 5, HNO 4. For other specific examples of peroxide compounds, reference can be made to the descriptions of “Peroxy” to “Pergabutin” in Kyoritsu Shuppan (1964). High oxidation number compound [the oxidation number of the central atom is two or more,
Refers to compounds whose oxidation numbers are not at their minimum. The higher the oxidation number rank, the greater the oxidizing power of the compound. As specific examples, NiO ₂ , N ₂ O ₄ , lead peroxide (PbO ₂ ), nitrogen peroxide,
Perchloric acid (HClO ₄ ), permanganic acid (HMnO ₄ ), periodic acid
(H ₅ IO ₆ ), high oxidation number sulfur compounds (chloramine, organic thiosulfonic acid compounds), FeCl ₃ , CuCl ₂ , MnO ₂ , KMnO
₄ , Na ₂ CrO ₄ ], halogen (Cl ₂ ,
Br ₂ , I ₂ ) and organic nitro compounds. These can be added alone or in combination of two or more. Among these, the peroxide and the compound having a high oxidation number are more preferable, and H ₂ O ₂ is more preferable. The compound has a standard electrode potential of 0.25 to 3.0 V, preferably 0.35 to
Compounds having a voltage of 3.0 V, more preferably 0.5 to 2.5 V are more preferred.

(Reducing Agent) Specific examples of the reducing agent include:
H ₂ , relatively unstable hydrogen compounds (eg, sodium borohydride, lithium aluminum hydride), lower oxides or salts of lower oxyacids (eg, CO, SO ₂ , sulfites), highly electropositive Metals (eg, alkali metals, Mg, Ca, Al,
Zn or their amalgams), salts of metals in low valence state (eg, Fe (II), Sn (II), Ti (III), Cr (II)],
Organic compounds with low oxidation degree (eg, aldehydes, sugars,
Formic acid, oxalic acid) and known reduction sensitizers (for example, thiourea dioxide, polyamine, amine borane) for AgX emulsions can be mentioned. Among these, a reducing agent that does not adversely affect the photographic properties of the reduction reaction product is preferable, and a salt of a lower oxide or a lower oxygen acid, the reduction sensitizer is preferable.
Sulfite and SO ₂ are more preferred. Compounds whose standard electrode potential is 0.2 to 3 V, preferably 0.5 to 2 V lower than the standard electrode potential of the oxidizing agent used are preferred. Here, the standard electrode potential indicates the electrode potential in the standard state of the half cell of the target substance when the standard hydrogen electrode potential is set to 0.0V.

For details on these oxidizing agents, reducing agents, oxidation, reduction, standard electrode potential, redox titration, and separation and purification, see (RD 1996), JP-A-8-69069, edited by The Chemical Society of Japan, Chemical Handbook. , Basics Chapters 10 to 12, Advanced Edition, Maruzen (1984), Chemical Society of Japan, New Experimental Chemistry Lecture, Volume 15, Oxidation and Reduction, Maruzen (1976), Minoru Imoto, Lecture Organic Reaction Mechanism Volume 10, Tokyo Kagaku Doujin (1965), edited by Yoshiro Ogata, Oxidation and Reduction of Organic Compounds, Nankodo (1963), JP-A-61-3134, Encyclopedia of World Science, "Redox", "Oxidation process""," Oxidizing agent ", Kodansha (1977
Year), Britannica International Encyclopedia, "Oxidation and Reduction", TBS Britannica (1988), Iwanami Lecture, Modern Chemistry 9, Acid-base and Redox, Iwanami Shoten (1980)
ian, AnalyticalChemistry, 4th edition John Wiley & Sons
(1986), Dictionary of Chemistry, Volume 3, pages 902-905,
Kyoritsu Publishing (1963), Electrochemical Handbook, Maruzen (1985),
The description in the Analytical Chemistry Handbook, Asakura Shoten (1992) can be referred to. Acids which can be used in the present invention,
For alkalis (bases), see Chemical Handbook, Basics,
You can refer to the description in Chapter 0, Maruzen (1984), HN
O ₃ , H ₃ PO ₄ , H ₂ SO ₄ , NaOH, KOH, and Na ₂ CO ₃ can be preferably used.

(I-4) Chemically modified gelatin. (A1) Amino group-modified gelatin. The amino group of the gelatin is chemically modified,
The relationship between the decoration rate and the divalent sulfur group content is preferably as shown in FIG.₁
Region, more preferably a_TwoRegion, more preferably a
_ThreeRegion, most preferably a_FourArea. a₁Territory of
The area is indicated by oblique lines. a₁The area is line a₁(Y₁= 6x₁−
210) and y₁= 0, y₁= 100, x ₁= 0, x₁=
The area surrounded by 40 is indicated. a_TwoThe area is line a_Two(Y₁=
6x₁-160) and y₁= 0, y₁= 100, x₁=
0, x₁= 35. a_ThreeRegion, a_Four
Each region is similarly (y₁= 10, y₁= 100,
x₁= 0, x₁= 25) line and line a_Three(Y₁= 6x₁−
100), (y₁= 10, y₁= 100, x₁= 1
0, x₁= 15) and line a_Four(Y₁= 6x₁Surround with -40)
Pointed area.

The chemical modification of the amino group means adding a reaction reagent to gelatin and reacting with the amino group to form a covalent bond or deamination. Specifically, for example, an acid anhydride (o-phthalic anhydride, succinic anhydride,
Trimellitic anhydride, acetic anhydride, maleic anhydride, benzoic anhydride, isatoic anhydride, etc.) or its acid, acid halide, compound having aldehyde group, compound having epoxy group, deaminating agent, active ester Compounds, isocyanate compounds, active halogen compounds,
Carbamoylating agents, compounds having an acrylic active double bond group, sultones (for example, butane sultone. Propane
sultone), a guanidine agent, carboxylazide, etc., preferably gelatin chemically modified with acid anhydrides and sultones, and more preferably trimellitized gelatin.

As a method for producing the gelatin, any of the following methods can be used in the order of each step of (1) chemical modification of an amino group, (2) oxidation, and (3) removal of a residual oxidizing agent. (1) → (2)
→ (3), (2) → (1) → (3), (2) → (3) → (1). Also,
After performing (1), a step of removing reaction by-products may be provided.

When the chemical modification rate of the number of amino groups of the gelatin before the start of grain formation is b ₄ , the chemical modification rate of the number of amino groups b at the start of coating of the silver halide emulsion, preferably after desalting of the emulsion. ₅ 0~0.8b _4, preferably 0~0.5b _4, we are more preferably at 0~0.2b _4. That is, the chemical modification group of the amino group is dissociated between the time when the grain formation is substantially completed and the time when the emulsion coating is started, preferably between the time when the grain formation is substantially finished and the time when the desalting step is completed. To reduce the chemical modification rate. This is because A during particle formation promotes particle growth.
The number of adsorbed groups on the gX particles is reduced, and after the particles are formed, the number of adsorbed groups is increased to enhance the protective colloidal properties of the particles. Thereby, the chemical sensitizing property and the spectral sensitizing property are improved, and the pressure fog resistance when the emulsion is coated on a support is improved. Here, “substantially” is added during particle formation.
It refers to the point in time when 60 to 100%, preferably 90 to 100% of Ag ⁺ is added.

In many cases, the dissociation may be effected by a hydrolysis reaction, and a highly ionic bond such as CO 2, CN, CP, CS, or CX is easily hydrolyzed. Hydrolysis of highly reactive bonds can occur with water alone, but it is preferable to add an acid (eg, HCl, H ₂ SO ₄ , HNO ₃ ) or a base to accelerate the reaction. H ⁺ coordinates to the negatively charged group of the ionic bond;
OH ^- it is to promote the bond cleavage coordinated to the positively charged group. In the case of adding an acid, the pH of the solution is preferably from 1 to 6, more preferably from 1.5 to 4. In the case of base addition, the pH of the solution is 7.5-7.5.
12 is preferable and 8.5 to 11 are more preferable. The temperature is preferably from 3 to 97 ° C, more preferably from 10 to 85 ° C.
Or adding hydrolase 1.0 to 10 ³ (mg / l) can be hydrolyzed by only. Usually, enzymes that hydrolyze ester bonds, peptide bonds, and glycosidic bonds are called esterase, peptidase, and glycosidase, respectively. In addition, they are classified into ether hydrolases, amidases, and hydrolases of (CC, halogen compounds, PN, SN, CP).

It is preferable to select a modifying group which is easily hydrolyzed. In this regard, maleyl groups are preferred. The maleyl groups undergo hydrolysis and dissociation in a low pH solution (preferably pH 1-5.8, more preferably pH 1.6-4). Therefore, the pH is adjusted to 6.0 to 12.0 during the formation of the particles, and when the formation of the particles is completed, the solution is lowered to a low pH to dissociate the groups. I just need. In the formula (A-1), R ¹ and R ^{2 each} have 1 to 10 carbon atoms.
Or a derivative thereof. Succinated gelatin is also stable at pH 6 or higher,
Since the succinated group is easily hydrolyzed in the region, the same handling can be performed, which is preferable. Generally, particles may be formed in the stable region of the modified gelatin and hydrolyzed in the unstable region of the modified gelatin. When the hydrolysis is performed immediately after the desalting treatment and immediately before the application, it is more preferable to perform the desalting treatment after the hydrolysis. For details of the hydrolase and the hydrolysis reaction, see Biotechnology Encyclopedia, “Hydrolase”, “Hydrolysis Reaction”, CMC (1986).
Year), Biochemistry Handbook, and Maruzen (1984).

(A-2) Imidazole group-modified gelatin. It is preferable that 3.0 to 98%, preferably 10 to 90%, more preferably 30 to 80% of the number of imidazole groups of the gelatin is chemically modified. Specific examples of the chemical modification are shown by the formula (I-2). The reaction occurs specifically for the imidazole group. 0.1 to control the pH value of the solution during the reaction.
It is preferable to use a phosphate buffer of 01 to 0.3 (mol / liter). The modification produces compounds (3) and (4) of formula (A-2). As the concentration of (2) increases, the value of (A-2)
The compound of the formula (5) is also produced, but its embodiment is also included. The molar formation ratio b ₈ = {(5) / [(3) + (4) + (5)]} of the compound (5) is preferably from 0 to 0.7, more preferably from 0 to 0.3.

Methionine content of the protein and imidazo
FIG. _TenArea of preference
A₁₁Is more preferable, and a₁₂Area is more preferred
A₁₃Is most preferable. a_TenArea is line a_Ten
(Y₁= 6x₁−210) and (y₁= 0, y₁= 10
0, x₁= 0, x₁= 40)
Then a₁₁Area is line a₁₁(Y₁= 6x₁−160) and
(Y₁= 5, y₁= 100, x ₁= 0, x₁= 35)
Refers to the area enclosed by the line, a₁₂Area is line a₁₂(Y₁=
6x₁−100) and (y₁= 5, y₁= 100, x₁=
0, x₁= 25) refers to the area surrounded by the line₁₃Territory of
Area is line a₁₃(Y₁= 6x₁−40) and (y₁= 5, y₁
= 100, x₁= 0, x₁= 15) Area surrounded by the line
Point to.

As a method for preparing the protein, it is possible to chemically modify the imidazole group first and then oxidize the divalent sulfur group. preferable. This is because the aqueous solution of the chemically modified imidazole group is not sufficiently stable. In addition, some of the chemical modifiers also easily react with a divalent sulfur group, and the divalent sulfur group may be chemically modified.
If the divalent sulfur group is oxidized first, it is prevented, and there is an advantage that the selectivity of imidazole group modification is further enhanced. The divalent sulfur group is oxidized, then the residual oxidant is removed, and then the imidazole group is chemically modified. Next, the solution is directly used, or after dehydration and concentration, further gelation and drying, and then added to the reaction vessel to form AgX particles.

The approximate comparison of the adsorption power of the imidazole group to the AgX particles with the adsorption power of the other functional groups is as follows. Therefore, if the number of methionine groups and the number of imidazole groups are controlled in the region shown in FIG. (Methionine group (1
00)> Imidazole group (80)> Amino group (2)> -COO ^- group
(2)] In addition, methyl-p-nitrobenzenesulfonate or iodo complex acid, which methylates an imidazole group having particularly high activity, can be preferably used as the modifier. Others
Diazonium-1H-tetrazole or a photosensitized oxidation method can also be used. For details, see "Methods in Enzymology, Acade
You can refer to the description of mic Press (1972). When chemically modifying both the amino group and the imidazole group, rather than chemically modifying the imidazole group first and then chemically modifying the amino group, first chemically modify the amino group and then modify the imidazole group. Chemical modification is more preferred. This is because the chemical modification to the already chemically modified group is prevented, and the selectivity of the modification is increased. Further, it is also preferable to remove the chemically modified group of the amino group after the chemical modification to the imidazole group. This is because the modification ratio of the imidazole group can be further increased.

[0033] In the case of an imidazole group-modified protein shown in Figure 2, is the same as described above (A1), when the chemical modification ratio of the imidazole groups of the protein before particle formation starts and the b _6, the AgX at coating start of the emulsion, preferably chemical modification ratio b ₇ of the imidazole base after desalting of the emulsion is 0～0.8B _6, preferably 0~0.5b
₆ , more preferably 0 to 0.2b ₆ . The compounds of formulas (3) and (4) of formula (I-2) are particularly unstable at pH 8 to 12, hydrolyze and tend to dissociate the modifying group. Regarding this embodiment, the description of (A1) can be referred to. Regarding these chemical modifications, the description in the literature described in the section (I-1) can be referred to.

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The content of the divalent sulfur group, sulfoxide group, sulfone group and sulfonate group, and the modification ratio of the amino group and imidazole group can be determined by the following methods. Gelatin is hydrolyzed to amino acids, neutralized, and analyzed with an amino acid analyzer to determine the content of each amino acid. This is determined by comparing with a previously prepared calibration curve for each amino acid. The target amino acid may be decomposed by a method in which the target amino acid is hardly decomposed, and the content of the target amino acid such as glycine may be determined with respect to the content of the amino acid. For details of the analysis method, see JP-A-8-82.
883, Instrument Analysis Guidebook, Chapter 8, Maruzen (1996)
Year), Journal of the Photographic Society of Japan, 58, 19-24 (1995)
Can be referred to. In addition, a method of measuring a change in molar spectral absorption coefficient of gelatin due to chemical modification, a method of dissociating a chemically modified group by hydrolysis, and a method of separating and quantifying dissociated molecules by liquid chromatography can be used.

(I-5) AgX particle formation. Ag ⁺ and X ⁻ are added to the dispersion medium solution containing the protein to form AgX particles. In this case, the equivalent sphere diameter (μ
m) is from 0.01 to 20, preferably from 0.03 to 10 (AgX composition of the whole particles is AgCl, AgB
r, AgI and a mixture composition of any ratio of two or more thereof can form AgX particles in the form of
In particular, 50 to 100% of the total projected area of all AgX grains,
Preferably 80 to 100%, more preferably 90 to 10
0% has a thickness (μm) of 0.01 to 0.50, preferably 0.01 to 0.30, and more preferably 0.01 to 0.2.
0, it is preferable to form the following tabular grains having an aspect ratio (diameter / thickness) of 1.5 to 500, preferably 2 to 500, more preferably 4 to 300. The tabular grains have a projected circle-equivalent diameter (μm) of 0.05 to 20, preferably 0.1 to 10, and a variation coefficient of the diameter variation (standard deviation of diameter / average value) of 0.01 to 0. 0.5 is preferable, 0.01 to 0.3 is more preferable, and 0.01 to 0.2 is preferable.
2 is more preferred. The AgX composition of the entire tabular grains is AgC
l, AgBr and a mixed composition having an AgI content of 0 to 40 mol% (A
gCl, AgBr and AgI in a mixed composition in any ratio of two or more.

(I-6) Tabular grains having a principal plane of {111} planes. (A1) Tabular grain structure. The outline shape of the main plane of the tabular grains is such that the maximum side ratio of one tabular grain [the side constituting the main plane (side length of the maximum side / side length of the minimum side) = b ₉ ] is 1 to 3, Preferably 1 to
Two hexagonal tabular grains and three or more triangular tabular grains can be mentioned. The tabular grains contain 2 to 5 parallel twin planes. Particles containing an even number of parallel twin planes often show the hexagonal shape, and particles containing an odd number of twin planes often show the triangular shape. In addition, circular tabular grains having rounded corners of these tabular grains can be mentioned. In this case, (the sum of the lengths of the sides of the polygon obtained by extending the straight line portion of the total / each side of the length of the linear portion of each side) linear portions ratios one particle = b ₁₀ is 0-1.0 can take, it referred to the case of 0-0.5 circular tabular grains, 0.5 <a b ₁₀ ≦ 1.0 and normal tabular grains.

FIG. 3 shows a cross-sectional structure of the tabular grain when cut perpendicular to the main plane, and shows the relationship between the thickness (d ₀ ) of the tabular grain and the position of the twin plane. The location of the parallel twin planes in Figure 3 _{[d 2 / (d 1 + d} 2 + d 3) ] = b ₁₁ 0.001
-0.98, preferably 0.01-0.9, more preferably 0.05-0.8. In this case, between 1 and ₂
It may have three twin planes. The variation coefficient (standard deviation of d ₂ value / mean value) of the variation of d ₂ value of tabular grains is 0.0
1-0.5 is preferable, and 0.01-0.3 is more preferable. The hexagonal tabular grains are more preferred. (Total area of {111} faces / total area of edge faces) of tabular grains = b ₁₂
Can be from 0 to 1.0, preferably from 0.1 to 0.8, and a non- {111} plane can be present on the edge surface. Non- ｛111
The {100} plane may be a {100} plane or {n10} plane (n = 1 to 5 and preferably 1). These preferably occupy 1.0 to 100%, preferably 5 to 50% of the total area of the edge faces of the tabular grains.

(A2) A method for preparing tabular grains. (B1) Seed crystal formation process. The following method can be mentioned as a method for preparing the tabular grains. (1) First, a diameter of 0.005 which does not substantially include twin planes
A method in which first fine particles of about 0.15 μm are formed, and then twin planes are formed on the fine particles to form twin seed crystals.
Here, the term "substantially free of twin planes" means that the total number of twin planes finally formed is 0.0 to 20.0, preferably 0 to 20.0.
Refers to twin plane formation of 5.0%. (2) A method of forming a twin plane from the time of forming the first fine particles. When forming the first fine particles, 20.1 to 100% of the total twin plane number, preferably 50 to 100%
%, More preferably 90 to 100%. (2) the smaller tabular grains having twin planes interval C ₂ is formed of, preferably.

Ag ⁺ and X ^- are added to the aqueous dispersion medium, and A
When gX particles are formed, the frequency of twin plane formation increases when the solution conditions are as follows. (1) Increase excess X ^- concentration. (2) Ag ⁺ and X ^- to increase the rate addition of (mole / min). (3) Decrease the concentration of the dispersion medium. (4) Decrease the pH. (5) When the concentration of the dispersion medium is the same, the frequency increases as the number of adsorbed groups on the AgX particles of the dispersion medium decreases.
For example, the frequency increases as the content of methionine groups or imidazole groups in gelatin decreases, or as the water solubility of gelatin increases as the amino groups are chemically modified. (6) Reduce the stirring speed. (7) If the concentration of the dispersion medium is the same, lower the molecular weight of the dispersion medium. (8) Lower the temperature. (9) Generate A
The frequency of the type of gX increases as the solubility decreases. The frequency is (AgCl <AgClBr <AgBr <AgBrI). (10) Excess
X ^- If the concentration is the same, X ^- is該頻degree of species (Cl ^- <Br
^- <I ^- a).

Further, at least one kind of the compound (A ⁰ ) is
By coexisting at the time of twin plane formation in (2), 25 to 100%, preferably 50 to 100% of the total number of twin planes finally formed.
100%, more preferably 80-100%, most preferably 90-100% of twin planes are formed. That is, when the other conditions are the same and the compound (A ⁰ ) is not allowed to coexist, the formation of twin planes corresponding thereto is eliminated. In the present invention, when the AgBr content (mol%) is 60 to 100, preferably 80 to 100 [or the AgCl content (mol%) is 0 to 4].
0, preferably 0 to 20]. AgCl content (mol%) of 50 to 10
In the case of 0, preferably 70 to 100, coexistence of A ⁰ is indispensable for forming the tabular grains. Compound (A ⁰ ) refers to the following compound. (1) 1 to 10 ⁴ onium bases per molecule
Group, preferably a compound (A ⁰ ) different from gelatin containing 2 to 10 ⁴ groups,

(3) One to seven iodine groups and one to one
Compound (A ² ) in which 7 —OH groups are substituted. (4) a nitrogen-containing heterocyclic compound, a compound containing 1-5 per molecule heterocyclic ring containing nitrogen atom or two during 4-7 membered ring (A ^3).
(5) Cyanine dyes (A ⁴ ). (6) a compound having a divalent sulfur-containing heterocyclic group (A ⁵ ), (7) a thiourea compound (A ⁶ ),
(8) amino thioethers (A ^7), (9) carbon atoms in total divalent sulfur-containing 25 or less of the organic compound (A ^8). The details of these compounds can be referred to the description in Japanese Patent Application No. 8-273952. (1) Description of (A ¹ ) Examples of general formulas of the onium base are shown in formulas (I-1) to (I-8).

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Where R¹~ R^ThreeAre the same
May be different from each other.
Represents an alkyl group, an alkenyl group, an aralkyl group, or an aryl group.
However, the number of hydrogen atoms is preferably 2 or less, more preferably 1 or less.
More preferably, 0 is more preferable. That is, carbon number 1-2
0 linear or branched alkyl group, cycloalkyl group, charcoal
An alkenyl group having 2 to 20 prime numbers, an aral having 6 to 20 carbon atoms
A kill group and an aryl group are preferred. These groups can be substituted
May be substituted with any group. Y^-Is an anion (negative charge
Atom or group of atoms). For example, acid group, OH
^-Group and halogen ion. Specific examples are
Cl^-, Br^-, NO_Three ^-, 0.5SO_Four ²⁻ , CH_ThreeC
OO^-And p-toluenesulfonate.
You. R^TwoIs R ¹Or R^ThreeCan form a ring closure with
You. In addition, the onium base has only one group in one molecule.
In the case of a compound or unless otherwise specified, (I-1) to
The free bond in formula (I-8) is R^FourAttached to the group. R
^FourThe group is R¹~ R^ThreeRepresents the same group as defined above.

The substitutable groups include the following groups (hereinafter referred to as
These are referred to as SB1). Halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (for example, methyl group, ethyl group, n-
Propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, allyl group, 2-butenyl group, 3-
Pentenyl group, etc.), alkynyl group (eg, propargyl group, 3-pentynyl group, etc.), aralkyl group (eg,
Benzyl group, phenethyl group, etc.), aryl group (for example,
Phenyl, naphthyl, 4-methylphenyl, etc.),
Heterocyclic group (for example, furyl group, imidazolyl group, piperidyl group, morpholino group, etc.), alkoxy group (for example,
Methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 2-naphthyloxy group, etc.), amino group (eg, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group, etc.) An acylamino group (eg, acetylamino group, benzoylamino group, etc.), a ureido group (eg, unsubstituted ureido group, N-methylureido group, N-phenylureido group, etc.), a urethane group (eg, methoxycarbonylamino group, Phenoxycarbonylamino group, etc.), sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl group, N-
Phenylsulfamoyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group, etc.), sulfonyl group (eg, mesyl group, tosyl group, etc.), sulfinyl group ( For example, methylsulfinyl group, phenylsulfinyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, Benzoyl group, formyl group, pivaloyl group, etc., acyloxy group (eg, acetoxy group, benzoyloxy group, etc.), phosphoric acid amide group (eg, N, N-diethylphosphoric acid amide group, etc.), alkylthio group (eg, methylthio group) Group, ethylthio group, etc.), aryl O group (eg, phenylthio group), cyano group, sulfo group, carboxy group, hydroxy group, phosphono group, nitro group, sulfino group, ammonium group (eg, trimethylammonio group), phosphonio group, hydrazino group, etc. is there. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the formula (I-1), R¹~ R^FourIs other than a hydrogen atom
In the case of the atom of⁺Is in the range of pH 1.0 to 12.0
Irrespective of pH, always N⁺Keep. But R¹
~ R ^FourWhen one or more of is a hydrogen atom,
At pH above the pKa value (Ka is the acid dissociation constant)
Hydrogen atoms dissociate as protons, not onium bases
The probability of becoming is increased. In this case, (the pKa + 0.3)
Or less, preferably the pKa or less, more preferably (the pKa
Ka-0.3) The compound was added to the reaction solution under the following pH conditions.
Point to coexist.

Two or more onium bases are as follows:
Preferably also be coupled 3-10 ³ group. (I)
Between the free bond via a divalent linking group L or R ¹
Linked through a group. L is an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, - S-,
—CO—, —NR ⁵ — (R ⁵ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred are alkylene and alkenylene. (Ii) bonding with a polymer chain. The onium bases to be bonded may be the same or different from each other, and may be an embodiment in which two or more groups of the above formulas (I-1) to (I-8) are linked. In that case, the total of various onium groups is 2 to
There are 10 ⁴ groups, preferably 3 to 10 ³ groups.

In particular, pKa within the pH range of 1.5 to 12.0
Having an acid dissociable group having a value (Ka is an acid dissociation constant)
Copolymers with mer are preferred. In general formula, (I
-9) is represented by the following equation. Where R⁸Is R¹~ R^ThreeWhen
Represents the same substituent. R⁹Is a substitution having the acid dissociable group.
Represents a group. n1 is 1 to 5000, preferably 1 to 10
00, more preferably an integer of 2 to 300, and n
2, n3 is an integer of 0 or more, preferably 1 to 10^Four,Than
Preferably 2 to 10^ThreeRepresents an integer. In this case, the pH
Is raised or lowered from the pKa value,
R⁹The degree of water solubility of the group is changed to increase the adsorptivity of the polymer.
It can be changed, which is preferable. For example, a -COOH group
In the case of such an acid group, its pKa value or more, preferably (pK
a-0.3) or more to adjust the pH to (-COO).
H → -COO^-+ H⁺) And the hydrophilicity of the group increases
Desorption of the polymer adsorbed on the AgX particles is promoted.
You. That is, when the polymer is no longer needed, the reaction solution
By adjusting the pH value, the polymer is converted from AgX particles.
There is an advantage that it can be desorbed and removed. -NH_TwoBase
In the case of such a base, its pKa value or less, preferably (pK
a-0.3) or less,_Two+ H⁺→
-NH_Three ⁺) And the water solubility increases. As the dissociative group
-SO_ThreeM, -SO_TwoM, -OSO_ThreeM, -COOM,
-NH _Two, -NHR¹, -NR¹R^Three, -SO_FourM,-
OPO_ThreeM_Two, (-O)_TwoPOOM can be mentioned,
Preferably -SO_ThreeM, -SO_TwoM, -COOM, -N
H_Two, -NHR¹, -OPO_ThreeM_TwoIt is. Where M is
H, alkali metal, or -NH_FourRepresents

A hydrophilic group is introduced into R ⁸ , and (n1 / n
2) It is preferable to change the ratio variously because the adsorption characteristics of the polymer can be changed almost continuously. As the water-soluble _{group, -OH, -CN, -CONH 2,} -COOC
_{H 3, - (CH 2 CH} 2 O) -, - CONH- can be exemplified. What is necessary is just to polymerize the monomer which has these groups, and synthesize | combine the compound represented by the said (I-9) formula. The (n1 / n2) ratio and the (n1 / n3) ratio are 1
A preferred ratio can be selected in the range of 0 ^-4 to 10 ⁴ , preferably 10 ^-3 to 10 ³ . Specific examples of the monomer include (I-11) to (I-16)

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The following can be mentioned. Where R ¹⁰ is R ⁷
It refers to any of ~R ^9. R ¹¹ represents an alkyl group having 1 to 10 carbon atoms. Specific examples of the polymer chain include a polyvinyl chain, a polystyrene chain, a polyamide chain, a polyester chain, a polyether chain, a polyether sulfone chain, a polyether ketone chain, a polysilicon chain, a polytriazine chain, a polyene chain, and a polyglycose chain. Can be listed,
Polyvinyl chains, polyamide chains, and polyester chains are more preferred. For details of the synthesis method of these polymer chains, see the Chemical Society of Japan, Chemical Handbook, Applied Chemistry, Chapter 8, Maruzen (1986), edited by Shuichi Suzuki et al.
Chapter VIII, Asakura Shoten (1993), edited by The Chemical Society of Japan, New Experimental Chemistry Course, Vol. 19, Maruzen (1978), U.S. Pat. No. 4,525,446 can be referred to.

Another specific example is a triazolium salt which is an onium embodiment of a triazole. For other details of the compound, see JP-A-4-33.
No. 5632 can be referred to. Among these, compounds containing a sulfonium base, a phosphonium base, a selenonium base, an arsonium base, a stibonium base, a stannonium base, an iodonium base, and a heterocyclic quaternary base are more preferred.

(2) Compound Containing Heterocyclic Nitrogen Quaternary Base Among the onium bases described in the above (1), a compound containing a heterocyclic nitrogen quaternary base is more preferable. The base is represented by the general formulas (II-1) to (II-4). The group is 1
Compounds containing one or more, preferably 2 to 300, more preferably 3 to 100 groups in the molecule. Where A ₁ -A ₄
Represents a group of nonmetallic atoms for completing the nitrogen-containing organic heterocycle, and may be the same or different. O,
It may contain N and S atoms, and the benzene ring may be condensed. The hetero ring composed of A _{1 to} A ₆ may have a substituent, and the substituents may be the same or different. As the substituent, the aforementioned SB1 can be mentioned. Preferred examples of A _{1 to} A ₄ include a 5- to 6-membered ring (eg, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, and the like). I can give it. (II-1) to (II-4) wherein the cation groups are linked to each other via a divalent linking group L or via a polymer chain (compound having two or more such cation groups). I can list them. The cationic groups to be linked may be the same or different. L represents the same divalent linking group as L described above. Preferred examples are alkylene,
Alkenylene can be mentioned. Examples of the polymer chain include the polymer chains described in the above (1). R
²¹ and R ²² represent the same groups as defined for R ¹ and R ³ above;
^- also the Y ^- represents a same group. Specific examples of the compound are shown in (II-11) to (II-15). That is, (I-
9) formula (B1-R ⁷⁾ repeating unit (II-
Examples in which cation-containing repeating units of 11) to (II-15) are introduced. N1, n2, n in this case
The definition of 3 is the same as the above.

(I). More preferred compounds have the general formula (II
-21) and (II-22). Wherein R ^23, R ²⁴ represents the same substituent as R ^1, R ^2, A ₅
-A ₈ is the same as A ₁ -A ₃ and represents a group of non-metallic atoms for completing the nitrogen-containing heterocyclic ring, and each may be the same or different. n11 represents 0 or 1, and is 0 in the case of an inner salt. n12 represents 0 or 1. L represents the same divalent linking group as described above. Y ^- is each as anions and the. Specific examples of the compound include (II-3)
1) to (II-35). For other details regarding the compound, see JP-A-8-29902 and 2-34.
You can refer to the description of the issue.

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[0056]

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(Ii). More preferred examples of the compound further include a compound represented by the formula (III-1). Here, R ³¹ represents the same substituent as R ¹ and R ^2, and R ^{32 to} R ³⁶ may be the same or different and each represents an H atom or a group which can be substituted with H atom. The above-mentioned SB1 can be mentioned as the substitutable group. ^R32 and ^R33 , ^R33 and ^R34 , ^R34 and ^R35 , ^R35 and R
³⁶ may be fused. However, at least one of R ³² to R ^36, an aryl group, aspect R ³¹ is an aralkyl group are more preferable. Y ^- is the Y ^- is the same as.
R ³² and R ^33, R ³³ and R ^34, R ³⁴ and R ^35, R ³⁵ and R ³⁶ are condensed to quinoline ring, an isoquinoline ring, may form a acridine ring. The following (III-2) to (III-8) show specific examples of the compound. For the other details of the compound, reference can be made to the description of Japanese Patent Application No. 7-148681.

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(Iii). More preferred examples of the compound further include a compound represented by the formula (I-9), and wherein the onium base is represented by the formula (II-3) or (II-4). Further, there may be mentioned compounds containing one or more heterocyclic nitrogen quaternary bases and one or more acyclic quaternary ammonium bases in one molecule. Preferably each is 1 to 10 ⁴
Group, preferably may be mentioned compounds containing 2-10 ³ group. For details of the compound, see World Patent 94-2.
No. 0551 can be referred to. For the method of synthesizing the compounds (1) and (2) and other details, see US Pat. No. 3,017,270 and European Patent 03.
No. 92092B1, U.S. Pat.
No. 25446, JP-A-2-293838, 7-30
No. 6489 can be referred to.

(3) One or more iodo groups and 1
Aromatic compounds substituted with at least -OH groups, iodine groups are preferably substituted with 1 to 8, preferably 2 to 5 groups, and hydroxy groups are substituted with 1 to 3 groups. preferable. Here, the aromatic compound refers to a carbocyclic compound having a benzene nucleus, and a compound in which another benzene ring or a heterocyclic ring is fused to a benzene ring (for example, naphthalene, anthracene,
Quinoline, indole). The aromatic ring includes the benzene nucleus, the condensed benzene ring, and the condensed heterocyclic ring, and preferably refers to the benzene nucleus and the benzene ring. More preferably 8-containing at least one iodo substituent
Hydroxyquinoline (the general formula is represented by the formula (IV-1)) is a phenol having at least two iodo substituents, and specific examples thereof are (IV-2) to (IV-5)
It was shown to.

(IV-2) 8-hydroxy-7-iodo-5-quinolinesulfonic acid (IV-3) 5,7-diiodo-8-hydroxyquinoline (IV-4) 5-chloro-8-hydroxy-7 -Iodoquinoline (IV-5) 8-Hydroxy-7-iodo-5-quinolinecarboxylic acid For details of these compounds see U.S. Pat.
Nos. 53 and 5411885 can be referred to.

(4) Nitrogen-containing heterocyclic compound A heterocyclic ring containing two or more nitrogen atoms in a 4- to 7-membered ring is
It is a compound containing at least one compound in the molecule, and preferably includes the following compounds. (A) Azaindenes More preferably, they are tetraazaindenes. Specific examples thereof include xanthoidoids [represented by the general formula (V-1), and specific examples thereof include xanthine and uric acid]; Indene (specific examples include purine, adenine, guanine and kinetin) can be mentioned. (B) Diazines (pyridazines, pyrimidines, pyrazines) Of these, substituted pyrimidines are preferred. As the substituent, the aforementioned SB1 can be mentioned. Specific examples of compounds include uracil, cytosine, thymine, and (V-2) to (V-
5) Compounds of the formula can be mentioned. For details of these compounds, see JP-B-5-40298 and JP-A-5-5-2.
No. 65111, No. 5-204077, No. 5-2326
12, JP-A-64-8325, edited by The Chemical Society of Japan, New Experimental Chemistry, Vol. 14, Chapter 9, Maruzen (1978).

(V-2) 4,5,6-triaminopyrimidine (V-3) 4,6-diaminopyrimidine-hemisulfate-monohydrate (V-4) 2,4-diamino-1,3 , 5-Triazine (V-5) 4,6-bis (methylamino) pyrimidine

(5) Cyanine dyes Dyes having a cationic structure in which two nitrogen-containing heterocycles are linked by a methine group —CH ＝ or a chain thereof, and have one or more acid groups, more preferably 1 to 2 It is preferable to have one. -SO ₃ and wherein acid groups ^-, -OSO ₃ ^-, -COO ^- refers to, preferably -SO ₃ ^- refers to the group. Preferred are imidocyanine, oxacyanine, thiacyanine, selenocyanine and their composite cyanine, and more preferred are imidocyanine and oxacyanine. For details of these compounds, see Research Disclosure, Volume 501, Item 36544, September 1994 (hereinafter, "RD.1").
994 "), edited by THJames, Theory of the Photographic Process,
Chapter 8, Macmillan (1977) can be referred to. Specific compound examples are shown in (VI-1) to (VI-
It was shown in 3).

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(6)-(9) Others disclosed in JP-A-62-29
No. 9961, a compound having a divalent sulfur-containing heterocyclic group, an organic compound containing divalent sulfur described in JP-A-63-41845, and JP-A-3-212639.
And thiourea described in JP-A-62-218959 and derivatives thereof. Preferred compounds are compounds other than the above (4), and more preferred compounds are
(1), (2) and (5), and most preferably (1) and (2).

A twinless normal crystal particle C _{10 having a} diameter of about 0.2 μm
And adding the onium compound to the emulsion containing a diameter of about 0.06μm in Muso crystal particles C _11, when aged under various solution conditions at 60-80 ° C., twinning promoted mechanism is seen by the onium compound. When Ag ⁺ is excessive, Ag ⁺
Is excessively adsorbed, adsorption of the compound is suppressed by Coulomb repulsion, and twin formation is hardly promoted. X ^- is
In a system excessively adsorbed on the surface of the AgX particles, the adsorption of the compound on the particle surface is promoted, the coalescence of the particles is promoted, and the twin plane formation is promoted. At a high pH of pH 8 to pH 11, gelatin is negatively charged and interacts with the onium group to deactivate the onium group, thereby suppressing twin plane formation. At a low pH of pH 1 to pH 5, the negative charge of gelatin decreases, the deactivation of onium groups decreases, and twin plane formation is promoted. Therefore, twin plane formation is promoted under medium to low pH and medium to low pX conditions. The twin plane formation is further promoted under the condition that a large amount of AgX fine particles are present and Ostwald ripening frequently occurs. Therefore, it can be seen that twin plane formation is more likely to occur at the time of nucleation at which much fine particle generation and Ostwald ripening occur. Considering the twin plane formation by a particle coalescence mechanism, many phenomena are easily explained. The effect of the pH and X ^- concentration is greater than that of X ^- concentration. These control agents promote twin plane formation during twin plane formation, and during grain growth,
It acts as a thinning agent to prevent an increase in the thickness of the tabular grains. Therefore, it is preferable to coexist at the above concentration even during the growth of the particles.

(B2) Ostwald ripening process. If the tabular grain number ratio is sufficiently high at the end of seed crystal formation,
The process can then proceed to the grain growth process. If not high enough, then Ostwald ripening to eliminate non-tabular grains,
Tabular grains are grown, and the tabular grain number ratio is set to 1.2 to 10 ^3.
Times, preferably 2.0 to 100 times. The following methods can be mentioned as the ripening method. (1) One-step aging method. One condition (temperature, pH, X ^- concentration, etc.)
Method to select the aging time optimally. (2) Two-step aging method. It comprises a first aging step and a second aging step under different conditions. It is preferable to increase the X ^- concentration in the second step by a pX value by preferably 0.1 to 2.0, more preferably 0.2 to 1.5, than the first step. First
The ripening pX value is preferably from 0.5 to 2.2, more preferably from 1.0 to 2.2.
1.8 is more preferred. (3) Aging method with 3 or more steps. It consists of three or more aging steps with different conditions. Here, pX = -log [X ^- concentration mol / liter].

In order to enhance the ripening effect, the AgX solvent is added in a concentration (mol / liter) of 1.0 to 10 ^-6 , preferably 0.2 to 10 s before the start of the ripening and before 30 seconds before the end of the ripening. ^-4 can be added. It is preferable to deactivate the AgX solvent after completion of aging. In the case of a basic AgX solvent (ammonia, ammonium salt, primary to tertiary amine compound), its ([pKa-0.2) to (pKa + 4)], preferably [(pKa) to (pKa)
Ka + 3)] at a pH of [(pKa -0.2) to (pKa-
6)]. Here, Ka is an acid dissociation constant, and is (pKa = -log Ka). It is also preferable to remove the AgX solvent out of the system by applying a known desalting method. The pH during the first aging is preferably from 1 to 5, more preferably from 1.5 to 4. In the low pH range, gelatin becomes positively charged and X
^- it is promoted adsorption to AgX grain surface adsorbed, gelatin -COO ^- group is -COOH, and the reduced water solubility of gelatin, from the fact that desorption process from AgX grains is suppressed,
This is because abnormal growth of tabular grains is suppressed, and tabular grains having a uniform size distribution can be obtained.

The following methods can be given as the aging method. (1) Ag ⁺ and X ^- how to do without the new addition of,
(2) Ag ^+, X ^- methods carried out while adding one or more a slow, (3) Musou crystal AgX fine particles (diameter 0.01~0.15μ
m) and aging in the presence. However, the case involving the addition of new Ag ⁺ is referred to as a growth process.
The temperature should be 5 ° C. or higher, preferably 10 ° C., for the seed crystal forming process.
It is preferable to ripen by raising the temperature by 70 ° C. If the desired tabular grain emulsion can be obtained only by the tabular seed crystal formation process, the tabular grain formation can be completed. Can be terminated. In many cases,
It goes through the process of (tabular seed crystal formation → ripening → growth), but the ripening process can be omitted.

(B3) Growth process. Ag ⁺ and X ^- is added and refers to the process of growing tabular seed crystals, it can be mentioned the following methods as a growth mode. (1) When the ratio of non-tabular fine particles is large, when Ag ⁺ and X ^- are added at a low rate, tabular grains grow with the disappearance of the fine particles due to Ostwald ripening. Therefore, as the tabular grains grow, the projected area ratio of the tabular grains increases. (2) previously prepared AgX fine grain emulsion 1 to 10 ⁴ times, is added preferably 2 to 10 ³ times, intermittently, or continuously, or in combination thereof. The ripening dissolves the fine particles and grows tabular grains. Diameter of the AgX fine particles (μm)
Is preferably 0.005 to 0.15, more preferably 0.01 to 0.10.

[0072] (3) Splash added (Ag ⁺ and X ^- rapidly added within a short time, a method to produce a new AgX particles in the reaction solution) 1 to 10 ⁴ times, preferably 2 to 10 ³
Performed intermittently. Newly generated fine particles are dissolved by aging, and tabular grains grow. The fine particles referred to in (2) and (3) are preferably the twin-free fine particles, and more preferably the defect-free fine particles. (4) Ag ⁺ and X ^- 1-100% of the critical addition rate, aspect preferably added at 10-90% of the addition rate. Here, the critical addition rate, at higher speeds Ag ⁺ and X ^- the addition of, refers to a rate of addition that new nuclei are generated. The higher the degree of supersaturation, the narrower the size distribution of tabular grains, but the greater the thickness. When it is desired to obtain thin tabular grains, it is preferable to add at a rate of 1.0 to 60%, preferably 1 to 40% of the critical addition rate.

In order to preferentially grow the edge surfaces of the tabular grains, a low supersaturation growth method by the fine particle addition method can be preferably used. Ag ⁺ and X ^- increasing the rate of addition of, increasing the degree of supersaturation of the solution approaches the growth rate of the large particles and small particles, the variation coefficient of the grain size distribution with the growth is small. However, since the driving force for growing the main plane is also increased, the growth rate in the thickness direction is also increased. Therefore, it is preferable to grow under optimum supersaturation conditions according to the purpose.

The particle growth controlling agent (g / liter) is used in a range of from 0.01 to 100, preferably from 0.1 to 100 minutes, preferably from 1 minute before the start of the particle formation to 1 minute before the end of the particle formation.
1 to 30 can be added. The controlling agent (B ⁰⁾ is weakly adsorbed on the edge face of the tabular grain, a compound to prevent abnormal growth of the edge surface, the molecular weight of the compound of 100 to 10 ^6. Specific compound examples include a polyalkylene oxide compound (B ¹ ), a polyvinyl alcohol compound (B ² ), a polyvinyl compound (B ³ ) having 1 to 10 ³ imidazole groups or benzimidazole groups in the side chain, an imidazole group or a benzil. Compounds containing imidazole groups and excluding proteins (B
⁴ ) and the details of these compounds can be referred to the descriptions in JP-A-8-82883, JP-A-8-339044, Japanese Patent Application Nos. 8-274729 and 10-9124. .

(I-7) Flat plate whose main plane is {100} plane
particle. (A1) Tabular grain structure. The following shape may be mentioned as the shape of the main plane of the tabular grains.
it can. (1) Right-angled parallelogram, adjacent to one tabular grain
Tangent side ratio (long side length / short side length) = b₁₃Is 1 to 1
0, preferably 1 to 5, more preferably 1 to 2. (2)
Of the four corners of the right-angled parallelogram, one to four, preferably
1 to 3 particles non-equivalently missing. That is, [(maximum missing
Area of fallen area / area of minimum missing part) = b₁₄Is 2.00∞
Particles. (3) Particles in which the four corners are equivalently missing. That is
The b₁₄Is 1.0 to 1.99. (4) 1.0 to 100% of the total area of the edge surface of the missing portion;
Preferably 5.0 to 80% of the particles are non- {100} faces.
Here, the non- {100} plane is the {111} plane or {n10} plane
And n = 1 to 5, preferably n = 1. (5) Main plane
At least two opposing sides of the four sides constituting
Is a particle whose outer convex curve. (6) Plate with (1)-(4)
Particles whose corners have been melted and rounded. In (1)
Right angle flat formed by extending the total length of the line part / the straight part
The sum of the lengths of the sides of the row quadrilateral) = b _FifteenIs 0.01-1.
0, preferably 0.3 to 0.90 particles.

(A2) A method for preparing tabular grains. (B1) Seed crystal formation process. The following method can be mentioned as a method for forming the tabular grains. (C1) By forming a non-uniform halogen composition during the formation of AgX grains, the integrity of the crystal structure is broken, and anisotropic growth defects are formed. The following method can be cited as an example of the non-uniform formation method. (1) As in (AgX ₁ | AgX ₂ ), the halogen composition is 1 in Cl content, Br content or I content.
A method of forming 1 to 10, preferably 1 to 5, layered structures differing by 0 to 100 mol%, preferably 30 to 100 mol%. (2) First, an AgX ¹ layer is formed, and then the halogen composition is X ¹
And a halogen salt that differs by that amount is added to cause halogen conversion. (3) X ₁ ^- Ag ⁺ and X ₁ in the halide salt solution ^{- -} different composition X ₃ and added, a method of forming a non-uniform mixed crystal. (4) Ag ⁺ and X ^- non foreign ions (metal ions,
Or complex salts thereof, SCN ^-, CN ^-), different element (S, Se,
Te) to form a layered structure with different contents (AgX ₁₀ | AgX ₂₀ )
A method for forming the defect.

(C2) AgX ₁ having an AgCl content of 50 to 100 mol%
A method of forming the defect by doping ^- from large atomic radius I ^- Cl in. (C3) an adsorbent C ⁰ to be adsorbed on the AgX grains with (g / l) 0.01 to 50, preferably from Ag ⁺ and X in the dispersion medium solution containing only 0.1-30 ^- by the addition of The tabular grains are formed. Here, the adsorbent C ⁰ indicates the following compound. (1) 2-10 ⁵ groups hydroxyl groups in one molecule, preferably a compound covalently bonded 5-10 ⁵ group, and compounds other than gelatin and protein (C ^1). (2) A compound (C ² ) having 1 to 10 nitrogen atoms having a resonance-stabilized π-electron pair. (3) the C ² 2 to 10 ⁵ cells per molecule, preferably 4 to 10 ^4, more preferably 8 to 10 ^four covalently bonded organic compound (C ^3). (4) Cyanine dye (C ⁴ ).

AgX C ⁰ non-uniformly adsorbed on the particle surface acts as a growth-promoting catalyst and promotes anisotropic growth, and the adsorbed C ⁰ causes crystal defects during lamination of Ag ⁺ and X ^−. A forming mechanism is conceivable. In the present invention, both are collectively referred to as anisotropic growth defects. If the desired tabular grain emulsion is obtained when the anisotropic growth defects are formed and the seed crystals of the tabular grains are formed, the tabular grain formation can be terminated. If the desired tabular grain emulsion is obtained at the end of the step, tabular grain formation can be terminated. In many cases, a process of (tabular seed crystal formation → ripening → growth) is performed, but the ripening process can be omitted.

(B2) Ripening process. When the tabular seed crystal ratio is low, Ostwald ripening is then performed to eliminate non-tabular grains and grow tabular grains, thereby increasing the tabular grain number ratio by 1.2 to 104 times, preferably 2 to ^4. it can be increased to 10 ^three times. The ratio is 1
%, Preferably 10% or more. In this case, the temperature is set at 5 ° C. or higher for the seed crystal forming process,
It is preferable to raise the temperature by 10 to 70 ° C. for aging. Use of AgX solvent during ripening, deactivation method after use, Ag ⁺ and X during growth ^- how the addition of a Sankounisuru things description of other ripening process and the subsequent growth process in general (I-2) Can be.

When growing the tabular grains, the surface
0 成長 Growth in the range of normal crystal grain formation with plane ratio of 50-100%
Preferably. For AgBr and AgBrI, this is silver
Growth under high conditions and fogging
You. To prevent this, a crystal habit control agent (D⁰)
(G / liter) 0.01 to 50, preferably 0.1 to 3
It is preferable that only 0 exists. D⁰ Examples of specific compounds
As described above, B¹~ B ^Four, Preferably B¹, B^ThreeRaise
I can do it.

(I-8) Others The gelatin promotes twin plane formation at the time of nucleation of tabular grains having {111} major planes, promotes tabular grain growth and extinction of non-tabular grains during ripening, and promotes tabular grain growth during growth. Promotes and is preferred. Therefore, in any of the steps of seed crystal formation, ripening, and growth, the total weight of the dispersion medium is 3%.
It is preferable to use 0 to 100%. The gelatin is formed after nucleation to 10 minutes before the completion of grain growth, preferably after nucleation.
It can also be added immediately before the start of grain growth. The gelatin promotes the formation of defects during nucleation of tabular grains having {100} major planes, promotes the growth of tabular grains and the disappearance of non-tabular grains during ripening, and promotes the growth of tabular grains during growth. I do. Therefore, in any of the steps of seed crystal formation, ripening, and growth, 30 to 100% of the total weight of the dispersion medium can be used. The gelatin is used after the nucleation to the completion of grain growth.
Minutes before, preferably after nucleation to just before the start of grain growth.

The gelatin can be added directly to the reaction vessel, or can be added to the added Ag ⁺ solution or X ^- solution. The adsorption power of amino group-modified alkali-treated gelatin with the same modification rate on AgX particles is in the order of (benzoylation> original gelatin>acetylation>phthalation>trimellitation> succination), and the introduction of phenyl groups. Increase the attraction force. Therefore, gelatin is modified with two or more types of modifiers, and the modification ratio of one modifier is 0.01 to 0.99, preferably 0.10 to 0.99.
It is preferable to adjust the attraction force by adjusting to zero. Regarding tabular grains having a principal plane of {111} planes, see JP-A-63-151618 and JP-A-58-11392.
No. 6, 63-11928, JP-A-2-28638.
Nos. 1-131541, 2-838 and 2-2
No. 98935, No. 3-121445, No. 8-6906
No. 9, 6-43605, 6-43606, 8
-82883, 2-34, 8-29902,
U.S. Pat. Nos. 5,176,992 and 5,061,617
Nos. 5,185,239 and 5,183,732
And Japanese Patent Application Nos. 7-146891 and 8-273952. Regarding tabular grains having a {100} major plane, see Japanese Patent Application No. 10-912.
Nos. 4, 9-259084, 8-42152, JP-A-8-339044, 8-272018, and 7
-234470, 7-146522, 6-30
No. 8648, European Patent 534,395 A1 can be referred to.

The diameter of a tabular grain refers to the diameter of a circle having an area equal to the projected area of the grain when the grain is observed with an electron microscope. The thickness refers to the distance between the major planes of the tabular grains.
As a method for detecting the amount of the remaining oxidizing agent, in addition to a potentiometric titration method using a reducing agent, a method for measuring the amount of oxygen when decomposed, a method for measuring iodine reduction titration, and a method for measuring the applied voltage / current curve of the oxidizing agent by polarography. For details, refer to the Chemical Dictionary, Kyoritsu Shuppan (1964), "Methods for Analyzing Hydrogen Peroxide", "Polarography", and "Polarographic Analysis". it can.

Benzoylation of the amino group of gelatin [Gel-
NHCO-phenyl groups], and the gelatin specified in FIG. 1 is particularly preferably used for forming AgBrI tabular grains having a {111} major plane. Here, the AgI content (mol%) is 0.1 to
20 is preferable and 1 to 10 are more preferable. Phenyl groups are compounds in which 1 to 4 of H of the phenyl group and the phenyl group are substituted with a group [(SB1)], which is substituted with an alkyl group having 1 to 10 carbon atoms. preferable. The adsorption of gelatin to AgX particles must not be too strong or too weak. The most desirable mode of forming AgX particles is obtained when the adsorption power is moderate.

Oxidation of gelatin is more than 0.3, preferably 0.5 to 5, apart from the isoelectric point pH value of gelatin.
It is better to go with H. In the vicinity of the isoelectric point, the molecules become thread-like, and oxidation of the group inside the thread does not proceed promptly. An embodiment in which 3.0 to 90%, preferably 10 to 80% of the number of hydroxyl groups of the gelatin is phosphorylated is also preferably used. This can be obtained by adding phosphorus oxychloride or phosphoric acid to a gelatin solution and subjecting hydroxyl groups to phosphoric acid esterification.

Chemical Sensitization The AgX emulsion grains of the present invention are preferably Sx sensitized, and more preferably further adsorb spectral sensitizing dyes, where Sx
Means sulfur, selenium, tellurium. As the Sx sensitizer, a conventionally known Sx sensitizer can be used, and specific examples thereof include thioureas, rhodanines, oxazolidines, polysulfides, selenoureas, phosphine selenides,
Selenoamides and thiosulfates can be mentioned, and the details can be referred to the description in the following literature. The AgX grains of the AgX emulsion of the present invention are preferably further gold sensitized. As the gold sensitizer, a conventionally known gold sensitizer can be used. For example, chloroauric acid, potassium chloroaurate, potassium or sodium aurithiocyanate (chloroauric acid: SCN ⁻ = 1: 1 to 1: 100 mol) Ratio), bromoauric acid, bromoiodic acid, gold sulfide, gold selenide, and the like. The ratio of (the number of moles of the gold sensitizer added / the number of moles of the Sx sensitizer) is preferably 4 to 0.2, and more preferably 2 to 0.3. The amount added to the AgX emulsion is 10 ^-2 to 1 respectively.
It is preferable to select an optimum amount from 0 ^-7 , preferably 10 ^-3 to 10 ^-7 mol / mol AgX.

As a desalting method of the AgX emulsion, Nudel washing method,
Dialysis method, ion exchange resin method, method of coagulating and sedimenting emulsion by adding coagulating sedimenting agent, method of utilizing coagulating sedimentation near the isoelectric point pH of modified gelatin, such as phthalated gelatin,
Examples include electrodialysis, ultrafiltration, centrifugation, centrifugal filtration, and hydrocyclone.
6 years) and the following literature. For centrifugation, filtration, and equipment, augmentation and centrifugation, Chemical Industry Co., Ltd. (1985), Separation and Purification Technology Handbook, No. 9
Chapter, Maruzen (1993) Scientific Instruments Overview, 96/97, 619-649
Page, the description of the Tokyo Scientific Instruments Association (1998).

As the spectral sensitizing dye, cyanine dyes (cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoporacyanine dye, hemicyanine dye, styryl dye, hemioxonol dye) are preferable. The dye may be one or more, preferably 1 to 10, of a solution, particles having a diameter of 0.01 to 10 μm or less alone or as a mixture with the dispersion medium and the surfactant, and a mixture with the solution containing the dispersion medium and the surfactant. Can be added. The amount of the dye added can be 1 to 120% of the saturated adsorption amount, and is preferably 10 to 98%.

Examples of the antifoggant include imidazoles, benzimidazoles, thiazoles, triazoles, tetrazoles, azaindenes, mercaptotetrazole, triazines, pyrimidines and triazines.

The obtained particles may be used as host particles to form epitaxial particles for use. Further, particles having dislocation lines of various shapes inside may be formed using the particles as a core. In addition, the particles as a substrate,
AgX layers having a different halogen composition from the substrate can be laminated to produce grains of any of various known grain structures. Regarding these, the description in the following literature can be referred to. As a method of forming the dislocation defect, a method of forming a halogen composition gap surface of AgX, adding one or more of Br ₂ and I ₂ , and then adding a reducing agent to generate X ⁻ , and halogen is added to the core particles. And a method of forming by conversion. Further, a shallow inner latent emulsion may be formed using the tabular grains as a core. Further, (core / shell) type latent particles can be formed.

The AgX emulsion grains thus produced were mixed with one or more other Ag
It can be used by blending with an X emulsion or by blending two or more kinds of emulsion grains of the present invention having different particle diameters. The blend ratio (moles of guest AgX emulsion / moles of AgX emulsion after blending) is preferably from 0.99 to 0.09.
The optimum ratio can be appropriately selected and used within the range of 1. There are no particular restrictions on the additives that can be added during the period from the start of grain formation of the emulsion to the end of coating, and any conventionally known photographic additives can be added in optimal amounts. For example, AgX solvent, doping agent for AgX particles (for example, Group 8 noble metal compounds, other metal compounds, chalcogen compounds, SCN compounds, etc.), dispersion media, antifoggants, sensitizing dyes (blue, green, red, infrared , Panchromatic, orthorectified, etc.), supersensitizers, chemical sensitizers (sulfur, selenium, tellurium, gold and Group VIII noble metal compounds, phosphorus compounds, rhodan compounds, reduction sensitizers alone and two kinds thereof) Combination of the above), fogging agents, emulsion sedimentation agents, surfactants, hardeners,
Dyes, color image forming agents, color photographic additives, soluble silver salts,
Examples include a latent image stabilizer, a developer (hydroquinone-based compound and the like), a pressure desensitization inhibitor, a matting agent, an antistatic agent, a dimensional stabilizer, and the like.

The AgX emulsion prepared by the method of the present invention can be used for all conventionally known photographic light-sensitive materials. For example, black-and-white silver halide photographic light-sensitive materials [for example, X-ray light-sensitive materials, printing light-sensitive materials, photographic paper, negative films, microfilms, direct positive light-sensitive materials, ultrafine particle dry plate light-sensitive materials (for LSI photomasks, shadow masks) , Liquid crystal masks)] and color photographic light-sensitive materials (eg, negative films, photographic papers, reversal films, direct positive color light-sensitive materials, silver dye bleaching photographs, etc.). Further, a diffusion transfer photosensitive material (for example,
Examples include color diffusion transfer elements, silver salt diffusion transfer elements), photothermographic materials (black and white, color), high-density digital recording materials, and holographic materials. A preferable amount of the applied silver amount is 0.01 g / m ² or more. AgX emulsion production method (grain formation, desalting, chemical sensitization, spectral sensitization, addition of photographic additives, etc.) and equipment, AgX
Particle structure, support, undercoat layer, surface protective layer, constitution of photographic light-sensitive material (eg layer constitution (silver / coloring agent) molar ratio, silver ratio between layers, etc.), product form and storage method, photographic additive There is also no limitation on the emulsification dispersion, exposure, development method, etc., and any conventional or future known techniques and modes can be used. For details of these, the description of the following literature can be referred to.

Research Disclosure (Research)
Disclosure), 176 volumes (item 17643) (12
Mon, 1978), Volume 307 (Item 307105, 11)
1989), Duffin, Photographic Emulsion Chemistry (Ph
otographic Emulsion Chemistry), Focal Press, New Y
ork (1966), Bill (EJ Birr), Stabilization of Photographic Silv
er Halide Emulsion), Focal Press
ess), London (1974), James (THJames)
, The Theory of Photographic Proc
ess) 4th edition, Macmillan, New York (1977)

P. Glafkides, Chemie et Physique Photographique, No. 5.
Edition, Edition
Usine Nouvelle, Paris (1987), 2nd edition, Paul Monterlu, Paris (1957), Zerikman et al. (VL Zel
ikman et al.), Preparation and coating of photographic emulsions (Making and Co.
ating Photographic Emulsion), Focal Press (1964
Year, KR Hollister, Journal of Imaging Sci
ence), Volume 31, pp. 148-156 (1987), JE Maskasky, Volume 30, pp. 247-254.
(1986) 32, 160-177 (1988), 3
Volume 3, 10-13 (1989),

Freezer et al., Eds., Fundamentals of the silver halide photographic process (Die Grundlagen Der Photographischen Prozesse)
Mit Silverhalogeniden, Akademische Verlaggesellschaf
t), Frankfurt (1968). JCIA Monthly Report 1984
Year, December issue, P. 18-27, Journal of the Photographic Society of Japan, 49
Vol. 7-12 (1986), Vol. 52, 144-166
(1989), 52, 41-48 (1989), JP-A-58-113926-13928, 59-9084.
No. 1, 58-111936, 62-99751, 60-143331, 60-143332, 61-
14630, 62-6251, EP 0699994
Nos. 4A1 to 0699951A1,

JP-A-1-131541, JP-A-2-838,
2-146033, 3-155539, 3-20
0952, 3-246534, 4-34544, 2-28638, 4-109240, 2-73334
6, 5-341417, 4-193336, 7-
181620, 6-215513, Other Japanese patents in the field of AgX photography, US patents, European patents, world patents, Journal of Imaging Science (Journal)
of Imaging Science), Journal of Photographic Scie
nce), Photographic Science and Engineerin
g), The Photographic Society of Japan, Abstracts of the Photographic Society of Japan, Inter
nationalCongress of Photographic Science and The
International East-West Symposium on the Factors
Collection of abstracts of Influencing Photographic Sensitivity.
Japanese Patent Application Nos. 6-104065 and 9-259084. The emulsions of the present invention are described in JP-A-62-269958 and 62-2.
No. 66538, No. 63-220238, No. 63-30
No. 5343, No. 59-142539, No. 62-253
No. 159, JP-A-1-131541 and 1-2976
No. 49, No. 2-42, No. 1-158429, No. 3-
No. 226730, No. 4-151649, No. 9-437
No. 66, Japanese Patent Application No. 4-179951, European Patent 0508
It can be preferably used as a constituent emulsion of the coating sample of the example of 398A1.

[0097]

Next, the present invention will be described in more detail by way of examples, but embodiments of the present invention are not limited thereto. Example 1 (Preparation of gelatin) 200 g of alkali-treated beef bone gelatin (a divalent sulfur group content of about 50 μmol / g, a deionized type in which positive and negative ions were removed and which is called Gel-0) was treated with water 14.
After swelling in 50 g, the mixture was heated to 50 ° C. and dissolved. A NaOH (1N) solution was added to adjust the pH to 6.0, and then water was added to make a total weight of 1700 g. This is called Gel-0 solution. Two of them are then heated to 40 ° C
, And 20 ml of a 3.1% by weight solution of H ₂ O ₂ was added thereto. The mixture was thoroughly stirred and mixed, and then capped. When 10 g of the sample was taken out and the residual H ₂ O ₂ amount was determined by a potentiometric current measurement method, about 40% of the added amount remained.

A NaOH (2N) solution was added to the gelatin solution, and p
After H6.5, the MnO ₂ particles (the projected circle equivalent diameter was 0.0
5 to 0.2 mm), and the temperature is kept at 38 ° C.
The remaining H ₂ O ₂ was decomposed for 2 hours with gentle stirring.
The gelatin solution was filtered through a membrane filter having a pore size of 5.0 μm to remove all the added MnO ₂ . Therefore, the remaining amount of MnO ₂ was 1.0% or less of the added amount.
The gelatin solution is referred to as Gel-1 solution. When the amount of residual H ₂ O ₂ was determined by an applied voltage / current measurement method, the residual amount was 0% of the added amount.
Amino acid analysis of the resulting gelatin revealed that 94% of the methionine was changed to methionine sulfoxide groups and the number of sulfone groups was 0. Therefore, b ₂ ≒ 1.0. The divalent sulfur group content was 3 (μmol / g). The solution was freeze-dried in vacuo, and the resulting gelatin was designated as Gel-1.

To the remaining one, an HNO ₃ solution was added to adjust the pH of the gelatin solution to 6.0, pure water was added, and a total amount of 2.0 was added.
kg and a temperature of 45 ° C. 2.7 g of ethoxyformic anhydride was added with stirring and reacted for 20 minutes. Further, the addition of 2.7 g of the anhydride and the reaction for 20 minutes were repeated, and a total of 2.7 × 4 = 10.8 g of the anhydride was added. After reacting for 20 minutes, it was concentrated by ultrafiltration.
The modification rate of the imidazole group was determined to be about 40% from the increase in the molar extinction coefficient at 240 nm of the gelatin solution after the reaction before the reaction. The solution was placed in a vacuum freeze dryer and dried. This was designated as Gel-2. Meanwhile, except not to MnO ₂ processing sequentially gelatin obtained in the same manner Gel-
3 and Gel-4.

(Formation of AgX Particles) A gelatin solution 10 [5.0 g of Gel-2, 1200 ml of H ₂ O, KBr 0.
8 g, containing 0.05 g of compound (III-2), pH 3.0]
, And the temperature was kept at 35 ° C, and the Ag-1 solution [100
The solution contains 6.0 g of AgNO ₃ and 0.8 g of Gel-2 in 0.2 ml, and 0.2 ml of HNO ₃ (1N) solution] and the X-1 solution [4.4 KBr in 100 ml].
g, 0.8 g of Gel-2 and 0.2 ml of NaOH (1N) solution] at 10 ml / min for 3 minutes. After stirring for 3 minutes, 0.2 g of Pluronic 31R1 (a block copolymer of polyethylene oxide and polypropylene oxide under the product name of BASF) was added to adjust the pH to 3.2. KB
25 ml of r-1 solution (containing 10 g of KBr in 100 ml) was added, the temperature was raised to 60 ° C., and the mixture was aged for 12 minutes. Gelatin solution 11 (20 g of Gel-2, 200 g of H ₂ O) was added, and a NaOH (1N) solution was added to adjust the pH to 7.5. Next, Ag-1
Solution 1 (containing 12 g of AgNO ₃ in 100 ml) and Solution X-11 (1
(Including 9.0 g of KBr in 00 ml) and an initial flow rate of 1.
5 ml / min, linear flow rate acceleration 0.25 ml / min for 40 minutes,
It was added while keeping the silver potential at -30 mV.

After stirring for 3 minutes, the temperature was increased to 35 ° C.
The mixture was adjusted to 2.0 and stirred for 3 hours. 30 ml of the emulsion was collected, centrifuged, the supernatant was removed, ultrafiltered, desalted,
Concentrated. The molar extinction coefficient at 240 nm of the solution was compared with that of the standard gelatin for comparison, and the modification rate of the imidazole group was determined to be 3% or less. However, the gelatin concentration was checked by elemental analysis. Therefore b ₇ ≦ 0.075b
It was ₆ .

A sedimentation agent was added to the remaining emulsion, and the pH was adjusted to 4.0.
Desalination was performed by sedimentation washing in the vicinity. Add Gel-0,
Redispersed at pH 6.5, temperature 40 ° C, pBr 2.6,
ureadioxide was 10 ^-4.5 mol added an aqueous solution (0.01%). Next, sensitizing dye 1 was added by 75% of the saturated adsorption amount. At this time, 1.0 ml of the emulsion was collected, and the transmission electron micrograph (TEM image) of the grain replica was observed. The following results were obtained. 97% of the total projected area of all AgX particles (hereinafter referred to as (SA)) has a thickness of 0.01 to 0.20 μm.
m, a diameter of 0.1 to 10 μm, a hexagonal tabular grain having an outline shape of a main plane having a maximum side ratio b ₉ = 1 to 2, and a tabular grain having an aspect ratio of 4 to 300.

The average thickness of the tabular grains was 0.10 μm, the average diameter was 1.3 μm, and the variation coefficient (standard deviation / average value) of the diameter variation was 0.15. The linear portion ratio of the particles was b ₁₀ ≒ 1.0. The tabular grains were cut by a microtome perpendicular to the main plane, and their low-temperature TEM images were observed to observe the twin plane positions. All b ₁₁ = 0.01 ~
0.2 and two twin planes.

The temperature of the emulsion was set to 50 ° C., and a gold sensitizer (aqueous solution of chloroauric acid: NaSCN = 1: 20 molar ratio) was added to 1.2 × 10 5
Only ^-5 mol / mol AgX was added, and 5 minutes later, chalcogenide sensitizer Sx1 was added only at 2 × 10 ^-5 mol / mol AgX. The temperature of the emulsion was raised to 60 ° C., ripened for 20 minutes, and then lowered to 40 ° C. The antifoggant TAI (4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene) was added to 3 × 10 ^−3.
Only mol / mol AgX was added, a thickener, a coating aid, and a hardener were added, and a protective layer together with the protective layer was applied to an undercoated PET (polyethylene terephthalate) base, followed by drying to obtain a coated sample 1.

Comparative Example 1a. Gel-2 added in Example 1
A coating sample (1a) was obtained in the same manner as in Example 1, except that Gel-4 was used. In the obtained particles, 96% of (SA) has a thickness of 0.1%.
01 to 0.20 μm, b ₉ = 1 to 2, aspect ratio 4 to
There were 300 tabular grains.

Comparative example (1b). A coating sample (1c) was obtained in the same manner as in Example 1 except that the operation of dissociating the modifying group after forming the particles was omitted. The obtained particles were obtained in Example 1.
Is the same as

Comparative example (1c). In the first embodiment, Gel-2 is replaced with Gel-3
The same operation as in Example 1 was performed except that the sample was coated (1c).
I got The obtained particles have a thickness of 0.01 to 96% of (SA).
0.20 μm, b ₉ = 1 to 2, aspect ratio 4 to 300
Were tabular grains.

Comparative example (1d). In Example 1, (Compound III-
A coated sample (1d) was obtained in the same manner as in Example 1 except that the addition of 2) was omitted. 96% of the obtained particles were tabular particles having a thickness of 0.01 to 0.20 μm, b ₉ = 1 to 2, and an aspect ratio of 4 to 300.

The coated samples obtained in Example 1 and Comparative Examples (1a) to (1d) were exposed for 0.1 second through a minus blue filter and an optical wedge that transmit light having a wavelength of 500 nm or more. Next, MAA-1 developer [Journal of Photographic Science, 2
3, 249-256 (1975)]
At 20 ° C. for 10 minutes. Stop according to the usual law,
After fixing, washing and drying, sensitometry was performed. Table 1 shows the obtained results [relative value of (sensitivity / granularity)] and the fog density. The higher the relative value, the better the photographic performance. The sensitivity was determined by the reciprocal of the exposure amount giving a density of (fog + 0.2). The graininess was determined by uniformly exposing the sample to an amount of light that gives a density of (fogging +0.2), performing the above-described development processing, and then, Macmillan, Theory of the Photographic Process, p. 619
The measurement was carried out according to the method described in (1).

After each film was bent along a cylindrical rod having a diameter of 3 mm, it was developed with MAA-1 developer at 20 ° C. for 10 minutes. The generated fog density was measured, and the results are shown in Table 1. From these results, the effect of removing the residual oxidizing agent (comparison of sample numbers 1 and 1a), the effect of modifying the imidazole group (comparison of 1 and 1c), and the effect of dissociating the modifying group after particle formation (1 and 1b) Comparison) and the effect of coexisting onium salt during nucleation (comparison between 1 and 1d) was confirmed.

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[0112]

[Table 1]

Example 2 (Preparation of gelatin) The procedure was the same as in Example 1 until the preparation of the Gel-1 solution. The gelatin solution was brought to 40 ° C, and the pH value was adjusted to NaOH (1
N) The solution was adjusted to pH 9.2, and a solution prepared by dissolving trimellitic anhydride at 12% by weight in dry acetone was stirred for 25 minutes.
It was added at a constant flow rate over a period of minutes. PH for another 25 minutes
Stirring was continued while maintaining at 9.2. Washing with ultrafiltration method,
Concentrated. When 10 g of the solution was taken out and subjected to formol titration, the trimerization ratio of amino groups in gelatin was 70%. Put the remaining solution in a vacuum freeze dryer,
Let dry. This was designated as Gel-5. On the other hand, gelatin similarly trimmed using Gel-3 was designated as Gel-6. The trimellitization rate was 70%.

(Preparation of AgX Emulsion) A gelatin solution 20 (0.70 g of Gel-1, 0.3 g of KBr, H ₂ O 1
Wherein 200 g, HNO ₃ placed adjusted with (1N) solution pH 2.5), and a constant temperature to 40 ° C., and 6g of AgNO ₃ in Ag-20 solution (100 ml, a Gel-1 0.8g, HNO ₃ ( 1N) solution and X-20 solution (4.3 g of KBr in 100 ml, KI 0. 0).
05 g, 0.8 g of Gel-1 and 0.2 ml of NaOH (1N) solution) were added simultaneously at 15 ml / min for 1 minute. 30 ml of KBr-1 solution was added, and the temperature was raised to 60 ° C. After aging for 10 minutes, a NaOH (1N) solution was added to adjust the pH to 9.1. 1
After aging for 2 minutes, gelatin solution 21 (20 parts of Gel-5)
g, H ₂ including O 200 g) was added, pH in HNO ₃ (1N) solution
Adjusted to 8.0. 3.3ml using Ag-20 solution and X-20 solution
Per minute for 12 minutes while maintaining the silver potential at -32 mV. Next, Ag-21 solution (2 AgNO ₃ in 100 ml)
0g) and X-21 solution (14.5g KBr in 100ml)
KI (including 0.19 g) with an initial flow rate of 1.8 ml /
At a linear flow rate of 0.21 ml / min for 35 minutes while maintaining the silver potential at -32 mV.

After stirring for 3 minutes, the temperature was increased to 35 ° C.
The mixture was stirred at 9.2 for 3 hours to dissociate the chemical modifying group.
30 ml of the emulsion was collected, centrifuged, the supernatant was taken out, ultrafiltered, desalted and concentrated. The solution was subjected to formol titration and the modification ratio was determined to be about 5%. However, the gelatin concentration of the solution was checked by elemental analysis. Thus it was b ₅ ≒ 0.07b _4.

When the TEM image of the replica of the obtained particles was observed, the following results were obtained. 97% of (SA) has a thickness of 0.01 to 0.20 μm, a diameter of 0.1 to 10 μm, and b ₉
= 1 to 2 and tabular grains having an aspect ratio of 4 to 300. Its average thickness is 0.055 μm and its average diameter is 1.5
μm, and the coefficient of variation in diameter variation was 0.16. b ₁₀ ≒ 1.0, b ₁₁ = 0.01 to 0.1,
The number of twin planes was two. Add a precipitant to the remaining emulsion,
At a pH of about 4.0, desalination was performed by a precipitation precipitation method. Gel-
0 was added, and the mixture was redispersed at pH 6.5, at a temperature of 40 ° C., and with pBr 2.6. Sensitizing dye 1 was added to the obtained emulsion at a saturated adsorption amount of 75%.
%. The temperature of the emulsion was adjusted to 50 ° C., and a gold sensitizer (aqueous solution having a molar ratio of chloroauric acid: NaSCN = 1: 20) was added to 1.2.
Only × 10 ⁻⁵ mol / mol AgX was added, and 5 minutes later, chalcogenide sensitizer Sx1 was added only at 2 × 10 ⁻⁵ mol / mol AgX. After raising the temperature of the emulsion to 60 ° C and aging for 20 minutes,
The temperature was lowered to ° C. Antifoggant TAI (4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene)
Only 10 ^-3 mol / mol AgX was added, a thickener, a coating aid, and a hardening agent were added thereto, and the resultant was coated on a subbed PET (polyethylene terephthalate) base together with a protective layer and dried to obtain a coated sample 2. .

Comparative Example 2a. A coated sample 2a was obtained in the same manner as in Example 2 except that Gel-1 was replaced with Gel-3 and Gel-5 was replaced with Gel-6. The particles obtained are 9 of (SA)
6% were tabular grains having a thickness of 0.01 to 0.20 μm, b ₉ = 1 to 2, and an aspect ratio of 4 to 300.

Comparative Example 2b. A coated sample 2b was obtained in the same manner as in Example 2 except that Gel-5 was replaced with Gel-3. The obtained particles have a thickness of 0.01 to 96% of (SA).
0.20 μm, b ₉ = 1 to 2, aspect ratio 4 to 300
Were tabular grains.

Comparative Example 2c. In Example 2, after forming the particles, p
A coating sample 2c was obtained in the same manner as in Example 2, except that the aging for 3 hours in H9.2 was omitted.

The coated samples obtained in Example 2 and Comparative Examples 2a to 2c were exposed for 0.1 second through a minus blue filter and an optical wedge that transmit light having a wavelength of 500 nm or more. Then MA
The film was developed with an A-1 developer at 20 ° C. for 10 minutes. Stopping, fixing, washing with water and drying were performed according to a conventional method, and sensitometry was performed. Table 2 shows the obtained results [relative value of (sensitivity / granularity) and fog density]. Each film has a diameter of 3
After bending along a cylindrical rod of 20 mm, the MAA-1
Developed at 10 ° C. for 10 minutes. Measure the generated fog density,
The results are shown in Table 2.

From these results, the effect of removing the residual oxidizing agent (comparison of Sample Nos. 2 and 2a), the effect of trimerizing and modifying the amino group (comparison of 2 and 2b), and the effect of dissociating the modifying group after particle formation (Comparison of 2 and 2c) was confirmed.

[0122]

[Table 2]

Example 3 (Preparation of gelatin) The Gel-1 solution was adjusted to 40 ° C., and the pH was adjusted to Na.
The pH was adjusted to 9.0 with an OH (1N) solution, and water was added to a total volume of 2 kg. 2
8 g of methylmaleic anhydride were dissolved in dry dioxane and added at constant flow rate over 20 minutes with stirring. The solution was adjusted to pH 9.0 with a NaOH solution and kept at 35 ° C. for 2 hours. Next, it was washed with water and concentrated by ultrafiltration. 10 g of the solution
Was taken out and subjected to formol titration. As a result, the maleation ratio of the number of amino groups in gelatin was 65%. The remaining solution was placed in a vacuum freeze dryer and dried. This is Gel-
7 was set. On the other hand, the maleated gelatin similarly using Gel-3 was designated as Gel-8. The maleation rate is 65%
Met. (Preparation of AgX emulsion) A gelatin solution 30 [Ge
l-7, 25 g of NaCl, 1.0 g of NaCl, 0.2 g of KBr, 2.0 g of compound 1 and adjusted to pH 4.5]
To constant temperature. Ag-30 solution with stirring (AgNO
₃ containing 10 g, Gel-1 0.8 g, HNO ₃ (1N) solution 0.2 ml) and X-30 solution [100 ml of 3.46 g of NaCl and Gel-
0.8 g of 1 and 0.2 ml of NaOH (1N) solution]
Per minute for 20 minutes. After raising the temperature to 50 ° C. and aging for 10 minutes, the Ag-30 solution and the X-30 solution were added simultaneously at 8 ml / min for 50 minutes while maintaining the silver potential at 120 mV. After stirring for 3 minutes, the temperature was lowered to 35 ° C and KBr-
Solution 1 (5 ml) is added, and 10 minutes later, KI-1 solution (KI in 100 ml)
10 g) was added. Here, compound 1 is PVA1
-S-PAA1, PVA1 is a polyvinyl alcohol group having an average degree of polymerization of about 500, -S- is a divalent sulfur group, and PAA-1 is polyacrylic acid having an average degree of polymerization of 62. The pH was adjusted to 3.0 with an HNO ₃ solution, and the mixture was maintained for 3 hours to dissociate the chemical modifying group. Take 30 ml of the emulsion, centrifuge,
The supernatant was taken out, subjected to ultrafiltration, desalted and concentrated.
The solution was subjected to formol titration, and the modification ratio of Gel-7 was determined to be about 5%. However, the gelatin concentration of the solution was checked by elemental analysis. Therefore, b ₅ ≒ 0.077b
_{Was 4} . When the TEM image of the replica of the obtained particles was observed, the following results were obtained. 93% of (SA) has a {100} plane as its principal plane, the outline of which is a rectangular parallelogram, a thickness of 0.01 to 0.20 μm, and a diameter of 0.1 to 10 μm.
m and b ₁₃ = 1 to 5, tabular grains having an aspect ratio of 4 to 300. The average thickness of the tabular grains is 0.05 μm,
The average diameter was 0.5 μm, and the coefficient of variation in diameter variation was 0.18. The edge surface was also {100}. Halogen conversion occurs at the corners and the thickness is 10 to 5
He was swollen by 0%. Add a precipitant to the remaining emulsion,
Desalting was carried out by a sedimentation washing method at around pH 4.0. Gel-0
Was added, and the mixture was redispersed with pCl 2.2 at pH 6.4, at a temperature of 40 ° C. Sensitizing dye 2 was added to the emulsion by 75% of the saturated adsorption amount. The temperature was raised to 55 ° C. and the hypo was reduced to 2 × 10 ⁻⁵ mol /
Only mole AgX was added, and then chloroauric acid was added at 10 ^-5 mole / mole AgX and aged for 25 minutes. Next, antifoggant 2 was added to 1
Only 0 ^-3 mol / mol AgX was added and the temperature was lowered to 40 ° C. A thickener, a hardener, and a coating aid were added, and the resultant was coated on a subbed PET base together with a protective layer, followed by drying.
Comparative Example 3a. Gel-1 added in Example 3 was replaced with Gel-3,
A coated sample (3a) was obtained in the same manner as in Example 3, except that l-7 was changed to Gel-8. In the obtained particles, 92% of (SA) has a thickness of 0.01 to 0.20 μm, a diameter of 0.1 to 10 μm, b
₁₃ = 1 to 5, and the tabular grains had an aspect ratio of 4 to 300. Comparative Example 3b. A coating sample (3b) was obtained in the same manner as in Example 3, except that the operation of dissociating the modifying group after the formation of the particles was omitted. The particles obtained are the same as in Example 3. Comparative Example 3c. A coated sample (3c) was obtained in the same manner as in Example 3, except that Gel-7 was replaced with Gel-3. In the obtained particles, 92% of (SA) has a thickness of 0.01 to 0.1%.
The tabular grains had a particle size of 20 μm, a diameter of 0.1 to 10 μm, b ₁₃ = 1 to 5, and an aspect ratio of 4 to 300. Example 3
Then, the coated samples obtained in Comparative Examples (3a) to (3c) were exposed for 0.1 second through a minus blue filter and an optical wedge that transmit light having a wavelength of 500 nm or more. Next, MAA-2 (MAA-1 developer
Developer with KBr replaced by equimolar NaCl)
Developed at 4 ° C. for 4 minutes. Stopping, fixing, washing with water,
After a drying treatment, sensitometry was performed. Table 3 shows the obtained results. After each film was bent along a cylindrical rod having a diameter of 3 mm, it was developed with MAA-2 at 20 ° C. for 4 minutes. The generated fog density was measured, and the results are shown in Table 3. Based on these results, the effect of removing the residual oxidizing agent (comparison of sample numbers 3 and 3a), the effect of maleic modification of the amino group (comparison of 3 and 3c), and the effect of dissociating the modifying group after particle formation (3 and 3b) Comparison) was confirmed.

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[0125]

[Table 3]

Example 4 Emulsions prepared in Examples 1 and 2 of the present invention were prepared by using JP-A-9-32
Samples to be used as emulsions for the respective emulsion layers of Sample 111 of Example 1 of No. 5450 were prepared and processed in the same manner as in Example 1 to obtain good results. Example 5 Emulsions prepared in Examples 1 and 2 of the present invention were prepared by using
Samples to be used as emulsions for each emulsion layer of Sample 101 of Example 1 of No. 5446 were prepared and processed in the same manner as in Example 1 to obtain good results. Example 6 The emulsion prepared in Example 3 of the present application was prepared by using JP-A-9-2883.
A sample to be used as the fifth layer emulsion of Sample 128 of Example 1 of No. 36 was prepared and processed in the same manner as in this example to obtain good results. Example 7 The emulsions prepared in Examples 1 to 3 of the present invention were prepared by
Samples to be used as emulsions for the respective emulsion layers of the light-sensitive material A of Example 1 of No. 9875 were prepared and processed in the same manner as in Example 1 to obtain good results.

[0127]

When the AgX emulsion of the present invention is coated in one or more layers on a support to produce a photographic light-sensitive material, the fog density is lower (sensitivity / granularity) as compared with the AgX emulsion prepared by the conventional method. An AgX photographic light-sensitive material having higher pressure resistance than the conventional method can be obtained.

[Brief description of the drawings]

FIG. 1. Divalent sulfur group content (μmol / g) of gelatin vs.
The preferred combination range of the chemical modification rate (%) of the amino group is shown.

FIG. 2: Divalent sulfur group content (μmol / g) of gelatin vs.
The preferred combination range of the chemical modification rate (%) of the imidazole group is shown.

FIG. 3 shows a cross-sectional structure when a tabular grain having a principal plane of {111} plane is cut perpendicular to the principal plane.

[EXPLANATION OF SYMBOLS] y ₁ represents the longitudinal axis of the x-y-axis view, x ₁ represents the horizontal axis. a _{1 to} a ₄ and a _{10 to} a ₁₃ each represent a boundary of the preferred combination range. 31, 32... The principal plane, 33... The twin plane closest to the principal plane 31, 34... The twin plane closest to the principal plane 32. d ₁ is the distance between 31 and 33, d ₂ is the distance between 33 and 34, d ₃ is the distance
32 and 34 intervals of, d ₀ represents the 31 and 32 intervals.

Claims (5)

[Claims] 1. A method for producing silver halide emulsion grains by adding silver ions and halogen ions to a dispersion medium solution containing at least a dispersion medium and water, wherein at least the total weight of the dispersion medium in the growth process of the grain formation is reduced. 30 to 100% is gelatin, and the gelatin is previously oxidized by adding an oxidizing agent to oxidize the divalent sulfur group, the content of the divalent sulfur group is reduced to 0 to 40 μmol / g, and the remaining unreacted unreacted A method for producing silver halide emulsion grains, wherein gelatin is added to the solution after 20 to 100 mol% of the oxidizing agent has been removed. 2. The method according to claim 1, wherein the oxidizing agent is a peroxy compound, and the removing is performed by bringing at least one of an alkali agent, a heavy metal having a specific gravity of 4.0 or more, the metal salt, and the metal oxide into contact with the remaining oxidizing agent. 2. The method according to claim 1, wherein the decomposition is carried out by accelerating a decomposition reaction of the oxidizing agent. Wherein the amino groups of the gelatin have been chemically modified, halogen according to claim 1, wherein the relationship of the chemical modification ratio and divalent sulfur group content and wherein it is the region of a ₁ in FIG. 1 Method for producing silver halide emulsion grains. 4. A tabular grain having a thickness of 0.01 to 0.5 μm and an aspect ratio (diameter / thickness) of 1.5 to 500 accounts for 50 to 100% of the total projected area of the silver halide grains. 2. The method for producing silver halide emulsion grains according to claim 1, wherein 5. The gelatin having a number of imidazole groups of 3.0.
2. The method according to claim 1, wherein -98% is chemically modified.
A method for producing silver halide emulsion grains as described above.