JP2002060626A - Water soluble polymer dispersion liquid, halogenated silver picture emulsion using the dispersion liquid and halogenated silver picture photosensitive material using the emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble polymer dispersion liquid in which a metal oxide particle is homogeneously dispersed even in a neutral pH range and to provide a halogenated picture emulsion and a halogenated silver picture photosensitive material showing an improved ratio of sensitivity to particle state by use of the water-soluble polymer dispersion liquid. SOLUTION: A water-soluble polymer dispersion liquid contains a metal oxide fine particle having an accumulated average diameter of 1 to 100 nm homegeneously dispersed therein and a low molecular weight gelatin of 0.001 to 200% based on the total mass of the metal oxide particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to the present invention, wherein the cumulative average particle size is 1 to
The present invention relates to a water-soluble polymer dispersion in which metal oxide fine particles having a diameter of 100 nm are uniformly dispersed, and as one application form thereof, a silver halide photographic emulsion having an improved sensitivity / granularity ratio, and a silver halide photographic emulsion using the same. Silver halide photographic light-sensitive materials.

[0002]

2. Description of the Related Art Metal oxide ultrafine particles having a cumulative average particle size of 1 to 100 nm are being applied to many functional materials due to their small particle size and large surface area. Is very strong, so that even when the dispersion of fine metal particles is added to an aqueous solution containing a polymer, cross-linking and aggregation are liable to occur, and it has been difficult to completely uniformly disperse the polymer in the polymer.

[0003] Further, as disclosed in JP-A-8-141388, a method of directly depositing particles in a polymer has a pH of 5 or less.
The following acidic or alkaline pH 7 or more, neutral pH
Could not prepare a uniform fine particle polymer.

[0004] Therefore, when the pH range is extremely restricted, particularly when used in a photographic material, it has been difficult to obtain a uniform neutral pH water-soluble polymer dispersion.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water-soluble polymer dispersion in which metal oxide fine particles are uniformly dispersed even in a neutral pH range, and furthermore, using this water-soluble polymer dispersion. Accordingly, it is an object of the present invention to provide a silver halide photographic emulsion and a silver halide photographic material having improved sensitivity / granularity.

[0006]

Means for Solving the Problems As a result of studying to solve the above problems, the present inventor has found that a water-soluble polymer dispersion having the following constitution is excellent in dispersibility of metal oxide fine particles, The inventors have found that a photosensitive material using a water-soluble polymer dispersion has excellent sensitivity and sharpness, and have completed the present invention.

(1) Fine metal oxide particles having a cumulative average particle diameter of 1 to 100 nm are uniformly dispersed, and low-molecular-weight gelatin is added in an amount of 0.001% to 200% of the total mass of the fine metal oxide particles.
% Water-soluble polymer dispersion.

(2) The water-soluble polymer dispersion according to (1), wherein the pH is from 5.0 to 7.0.

(3) 75 to 100% by mass of the composition of the metal oxide fine particles has an isoelectric point at which the difference from the pH value of the water-soluble polymer dispersion is -2.0 to 2.0. The water-soluble polymer dispersion according to (1) or (2), which is occupied by a metal oxide.

(4) The metal oxide fine particle water-soluble polymer dispersion according to any one of (1) to (3), wherein the water-soluble polymer contains non-low molecular weight gelatin.

(5) The non-low molecular weight gelatin has a molecular weight of about 20 in the molecular weight distribution measured according to the PAGI method.
The water-soluble polymer dispersion according to claim 4, wherein the high molecular weight component of not less than 10,000 is in the range of 3% or less.

(6) The water-soluble polymer dispersion according to any one of (1) to (5), wherein the low-molecular-weight gelatin is chemically modified.

(7) The metal oxide is at least one selected from the group consisting of titanium oxide and zirconium oxide, any one of (1) to (6).
Item 10. The water-soluble polymer dispersion according to item 8.

(8) At least a part of the metal oxide fine particles is surface-treated, and at least 60% by mass of the total surface-treated substance is an oxide of the same type. The water-soluble polymer dispersion according to any one of (7).

(9) The method according to (8), wherein at least a part of the metal oxide fine particles is surface-treated, and 80% by mass or more of the total surface-treated substance amount is an oxide of the same type. A water-soluble polymer dispersion as described in the above.

(10) At least a part of the metal oxide fine particles is surface-treated, and the total amount of the surface-treated substance is 2% or less of the total mass of the fine particles.
(7) The metal oxide fine particle water-soluble polymer dispersion according to any one of (7).

(11) Any one of (1) to (10)
A solid composition obtained by drying the water-soluble polymer dispersion liquid described in the paragraph.

(12) Any one of (1) to (10)
Wherein the coefficient of variation of the equivalent circle diameter of all silver halide grains is 40% or less, and 50% or more of the total projected area satisfies the following (i) and (ii): A silver halide photographic emulsion characterized by being occupied by silver halide tabular grains.

(I) Tabular silver iodobromide or silver iodochlorobromide grains having a (111) plane as a main surface. (Ii) A circle equivalent diameter of 1.0 μm or more and a thickness of 0.01 μm or more and 0.1 μm or less. The silver halide photographic emulsion according to (12), wherein the coefficient of variation is 25% or less.

(14) The silver halide photographic emulsion according to (13), wherein the coefficient of variation is 15% or less.

(15) A silver halide photographic material having at least one layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to any one of (12) to (14) in at least one of the silver halide emulsion layers.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION In the water-soluble polymer dispersion of the present invention, metal oxide fine particles having a cumulative average particle size of 1 to 100 nm are uniformly dispersed. 001 to 200%.
In the present invention, the low molecular weight gelatin functions as a dispersion stabilizer.

The state in which the particles are uniformly dispersed in the present invention refers to a state in which the particles do not contain coarse particles of 1 μm or more, retain the colloidal dispersion system, and do not cause layer separation. This can be confirmed by the fact that the dispersion does not separate and cause layer separation even when left at room temperature for one day. Further, the water-soluble polymer dispersion in the present invention has an isolated polymer or polymer ion as dispersed particles, the dispersion medium is a liquid phase mainly composed of water, and the system is thermodynamically stable. Such a molecular colloid. In addition, the cumulative average particle size referred to in the present invention is a particle size at a point where the particle size distribution becomes 50% when the volume of the entire particle is 100%. Nikkiso's Micro Truck UPA
For example, it can be measured by a measuring device using a dynamic light scattering method. Since it is often impossible to accurately measure the fluctuation of the hydrodynamic radius in the polymer, the measurement is performed from the particle size distribution of the aqueous dispersion by selecting an appropriate pH.
In the present invention, the water-soluble polymer preferably contains non-low molecular weight gelatin. Here, the non-low molecular weight gelatin refers to gelatin having a weight average molecular weight of more than 60,000.

The method for producing gelatin that can be used in the present invention can be prepared by a generally used method for producing photographic gelatin except that the molecular weight distribution is defined in the scope of the present invention. For example, it is described in the Photographic Society of Japan, “Basic silver halide photography in photographic engineering” (Corona), pp. 122-124.

The photographic gelatin that can be used in the present invention can be produced from collagen contained in bovine bone, cow skin, pig skin and the like, and can be extracted by treating the collagen with an acid or an alkali. There is no restriction on the raw material, but it is preferable to use cow bone or cow hide.

The gelatin used in the present invention may be acid-treated gelatin or alkali-treated gelatin, but alkali-treated gelatin is preferred. In the case of alkali-treated gelatin, sub-α (low molecular weight),
α (molecular weight of about 100,000), β (molecular weight of about 200,000), γ (molecular weight of about 300,000), void (high molecular weight) and the like.
The ratio of the gelatin components in the present invention, that is, the molecular weight distribution, is measured by gel permeation chromatography (hereinafter referred to as "GPC method") according to the internationally determined PAGI method. Regarding this method, Takashi Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, Kei Tao
7, No. 4, 1984, pp. 237-247.

Specific conditions for measuring the molecular weight distribution of gelatin according to the present invention are described below.

(Measurement conditions) Column: Shodex Asahipak GS-620 7G (8 mm ID × 500 m
m) × 2 Guard column: Shodex Asahipak GS-1G 7B Eluent: 0.1 mol / l phosphate buffer (pH 6.8) Flow rate: 0.8 ml / min Column temperature: 50 ° C. Detection: UV230nm Sample injection volume: 110 μl (0.2% (Phosphate buffer solution) The GPC curve obtained by taking the retention time (Retention Time) on the horizontal axis and the absorbance on the vertical axis firstly shows the peak of the exclusion limit, then the β component and α component peaks of gelatin, Furthermore, as the retention time becomes longer, the shape becomes like a tail.

The proportion occupied by the high molecular weight component having a molecular weight of 2,000,000 or more in the present invention is determined by calculating the proportion occupying the entire exclusion limit peak area. Specifically, a perpendicular line is drawn from the minimum point of the GPC curve appearing at about 17th minute of the retention time to the horizontal axis, and the proportion of the high molecular weight side portion (high molecular weight component) from the perpendicular line to the entire area is calculated. .

In the present invention, the non-low molecular weight gelatin is preferably one in which a high molecular weight component having a molecular weight of about 2,000,000 or more is controlled to 3% or less. If the high molecular weight component exceeds 3%, the coatability of the water-soluble polymer dispersion liquid rapidly deteriorates, which is not preferable. In order to obtain suitable coatability, it is particularly preferable that the high molecular weight component having a molecular weight of 2,000,000 or more is 1% or less.

When metal oxide fine particles having a cumulative average particle diameter of 1 to 100 nm are dispersed in a water-soluble polymer, cross-linking aggregation is likely to occur between the particles due to the small size of the fine particles, and the aggregation significantly deteriorates uniform dispersibility. And is not preferred. However, the present inventor has adjusted the pH of the aqueous dispersion of metal oxide fine particles to such a value that the metal oxide has charge repulsion, so that the aqueous dispersion of metal oxide fine particles does not cause crosslinking and aggregation of the particles, and It has been found that the addition of a low molecular weight gelatin to a dispersion stabilizer to such an extent that the charge state is not changed significantly improves the cohesiveness.

The low molecular weight gelatin used in the present invention is
It is desirable that the gelatin has a weight average molecular weight of 60,000 or less, preferably 30,000 or less, and 2,000 or more, preferably 5,000 or more. The low molecular weight gelatin used in the present invention can be usually prepared as follows. A commonly used gelatin having an average molecular weight of 100,000 (hereinafter also referred to as "normal molecular weight gelatin") is dissolved in water, and a gelatin-decomposing enzyme is added to gelatinize the gelatin molecules. See RJCox Photographic Gelatin II, Academic
Press, London, 1976, p.233-251, p.335-346 can be referred to. In this case, since the binding position at which the enzyme is decomposed is fixed, low molecular weight gelatin having a relatively narrow molecular weight distribution can be obtained, which is preferable. In this case, the longer the enzymatic decomposition time, the lower the molecular weight. Others
There is also a method of performing hydrolysis by heating in a low pH (pH 1 to 3) or high (pH 10 to 12) atmosphere.

In order to improve the coatability of the metal oxide fine particle water-soluble polymer dispersion of the present invention, low molecular weight gelatin may be chemically modified. The low molecular weight gelatin used as the dispersion stabilizer is preferably contained in an amount of 0.001% by mass to 200% by mass based on the total mass of the metal oxide fine particles. 0.
When the content is less than 001% by mass, the ability of low-molecular-weight gelatin to prevent cross-linking aggregation is insufficient and cross-linking aggregation occurs. On the other hand, if the low molecular weight gelatin is more than 200% by mass, the coating property is remarkably reduced, which is not preferable. The preferred pH of the water-soluble polymer dispersion of the present invention is from 5.0 to 7.0.

Next, the isoelectric point of the metal oxide fine particles used in the present invention will be described.

The water-soluble polymer dispersion of the present invention has a remarkable dispersion stabilizing effect particularly on metal oxide fine particles which easily aggregate in a neutral region. Particularly, metal oxide fine particles having an isoelectric point of pH 5 to 7 are preferable. Metal oxides having such properties satisfying the object of the present invention include titanium oxide and zirconium oxide. The inventor has
75 to 100% by mass in the composition of the metal oxide fine particles
But the difference from the pH value of the water-soluble polymer dispersion was -2.
It has been found that a significant stabilizing effect occurs when occupied by a metal oxide having an isoelectric point of a value corresponding to 0 to 2.0. The fine particles used in the present invention may be prepared by dispersing a powder, or a commercially available slurry may be used. As the inorganic fine particles dispersed in the polymer,
Oxide particles of a metal (for example, aluminum, titanium, zirconium, antimony, yttrium, zinc, tin, and magnesium) are used. The microparticles are used as a powder or a colloidal dispersion. Water is used as the dispersion medium.

In order to obtain a dispersion of solid fine particles, a known disperser can be used. Examples of the dispersing machine include a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill and a roller mill. The disperser is disclosed in JP-A-52-92716.
And International Patent Publication No. 88/077944. Vertical or horizontal media dispersers are preferred. Next, a preferred surface state of the metal oxide fine particles will be described.

Since the cumulative average particle size of the metal oxide fine particles used in the present invention is 1 to 100 nm, the interparticle force is very strong and aggregation is easily caused. The surface charge of a metal oxide changes in accordance with the pH, and is positively charged on a sufficiently acidic side and negatively charged on a sufficiently basic side. Or there is a difference between positive and negative,
It is preferable that the surface composition of the particle surface is uniform because secondary aggregation easily occurs easily and uniform dispersibility of the particles is impaired. The surface of the particles is often subjected to a surface treatment with a metal oxide. The surface treatment process is described in “Titanium oxide physical properties and applied technology” published by Gihodo, pages 28-29. A predetermined amount of A
1, a salt aqueous solution of Si, Ti, Zr, Sb, Sn, Zn or the like is added, an alkali or an acid for neutralizing the solution is added, and the surface of the particles is coated with a hydrated oxide to be formed.

When the surface of the particles is subjected to a surface treatment, it is preferable that at least 60% by mass of the total surface treatment substance is treated with the same type of oxide, and at least 80% by mass is treated with the same type of oxide. More preferably, it is performed. The composition ratio can be detected by X-ray fluorescence measurement.

It is also effective to keep the surface charge uniform without performing any surface treatment. In that case, it is preferable that the total amount of the surface treatment substance of the metal oxide fine particles is 2% by mass or less of the total mass of the fine particles. Here, the total amount of the surface treatment substance means the total mass of the oxide used for the surface treatment.

The dried product obtained by molding the metal oxide fine particle water-soluble polymer dispersion of the present invention by a method such as coating can be applied to various uses. Next, the form of a silver halide photographic emulsion and a silver halide color photographic light-sensitive material which are mentioned as an effective application method of the water-soluble polymer dispersion of the present invention will be described.

The emulsions of the present invention and photographic emulsions other than the present invention used in combination therewith are described in Grafkid, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkids,
Chemie et Physique Photog
raphique, Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographi).
c Emulsion Chemistry (Foca
l Press, 1966)), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL.
Zelikman et al. , Making an
d Coating Photographic Em
ulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

US Pat. Nos. 4,334,012, 4,301,241, and 4,150,994, in which silver halide grains which have been previously precipitated are added to a reaction vessel for preparing an emulsion. Is optionally preferred. These can be used as seed crystals,
It is also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at a time, adding in a plurality of times or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface. A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in U.S. Pat. Nos. 3,477,852 and 4,1.
No. 42,900, European Patent 273,429, No. 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

As a method of grain growth, besides a method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, British Patent No. 1,469,480 and US Pat.
The particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. Nos. 0,757 and 4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 3,785,777, West German Patent 2,5
No. 56,885 and 2,555,364. Silver halide solvents are useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, or can be added together with the halide salts, silver salts or peptizers, and added to the reactor. Can also be introduced. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As the ripening agent, for example, ammonia, thiocyanate (for example, rhodancali, rhodan ammonium), organic thioether compound (for example, US Pat. Nos. 3,574,628, 3,021,215, No. 3,057,724, No. 3,038,805,
Nos. 4,276,374 and 4,297,439
No. 3,704,130, No. 4,782,01
No. 3, the compound described in JP-A-57-104926. ), Thione compounds (for example, JP-A-53-8240)
No. 8, No. 55-77737, U.S. Pat.
No. 863, compounds described in JP-A-53-144319, and silver halide grains described in JP-A-57-202531. Mercapto compounds and amine compounds (for example, JP-A-54-100717).

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives ;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. Enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

A method of adding a chalcogen compound during the preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present. The silver halide grains of the present invention may be used for at least one of chalcogen sensitization such as sulfur sensitization and selenium sensitization; noble metal sensitization such as gold sensitization and palladium sensitization; It can be applied in any process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, No. 4. Edition, published by Macmillan, 1
977, (TH James, The Theor)
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67-76, and can be carried out using Research Disclosure (hereinafter referred to as "RD"), Volume 120, 19
April 74, 12008; RD, Volume 34, June 1975
Moon, 13452, U.S. Patent Nos. 2,642,361, 3,297,446, and 3,772,031,
Nos. 3,857,711 and 3,901,714,
Nos. 4,266,018 and 3,904,4
No. 15, and pAg 5-10, pH 5-8 and temperature 30-30 as described in GB 1,315,755.
At 80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers.

In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known materials such as gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are R ₂ Pd
It is represented by X ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, preferably a chlorine, bromine or iodine atom. Specifically, K ₂ PdC
_{l 4, (NH 4) 2} PdCl 6, Na 2 PdCl 4,
(NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ P
dCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and U.S. Pat. Nos. 3,857,711 and 4,266.
018 and 4,054,457 can be used.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization auxiliary. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757, JP-A-58-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol per mol of silver halide.
The preferred range of the palladium compound is 1 × 10 ⁻³ to 5
× 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ^−2.
−6 . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mole of silver halide.
It is 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol. Selenium sensitization is a preferred sensitization method for the emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium and selenoureas (for example, N, N-dimethylselenourea, N, N-
Selenium compounds such as diethylselenourea), selenoketones, and selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a pAg 1 to 7 low pAg atmosphere called silver ripening, or a pH 8 to 10 called high pH ripening. Either a method of growing or ripening in a high pH atmosphere of 11 can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted. Known reduction sensitizers include, for example, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount.
The range of 10 ^-7 to 10 ^-3 mole per mole is suitable.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth.
It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated in, for example, silver halide, sulfide
May form silver salts that are hardly soluble in water such as silver and silver selenide.
And may form a silver salt easily soluble in water such as silver nitrate.
No. The oxidizing agent for silver can be inorganic or organic.
There may be. As the inorganic oxidizing agent, for example, Ozo
Hydrogen peroxide and its adducts (eg, NaBO)
₂・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂,
Na₄P₂O₇・ 2H₂O₂, 2Na₂SO₄・ H₂O
₂・ 2H₂O), peroxyacid salts (eg, K₂S₂O
₈, K₂C₂O₆, K₂P₂O₈), Peroxy complexation
Compound (for example, K₂[Ti (O₂) C₂O₄] ・ 3H₂
O, 4K₂SO₄・ Ti (O₂) OH ・ SO₄・ 2H₂
O, Na₃[VO (O₂) (C₂H₄)₂] ・ 6H
₂O), permanganate (eg, KMnO)₄),Black
Oxalates (eg, K₂Cr₂O ₇Oxyacids, such as
Halogen elements such as iodine and bromine, perhalates (eg
For example, potassium periodate), high valent metal salts (eg,
For example, potassium hexacyanoferrate) and thiosulfur
There are phosphates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (eg, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example. Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents for thiosulfonates and organic oxidizing agents for quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as titraazaindenes) and pentaazaindenes;
Many compounds can be added.

For example, US Pat. No. 3,954,474
No. 3,982,947, Japanese Patent Publication No. 52-2866
No. 0 can be used. One of the preferred compounds is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus,
Thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus are applied it can. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or composite merocyanine dye has a ketomethylene structure as a nucleus.
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-4936, 53-12
No. 375, JP-A-52-110618, JP-A-52-10
No. 9925.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4225666, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
It can be used at 10 ⁻⁶ to 8 × 10 ⁻³ mol,
More preferred silver halide grain size 0.2 to 1.2 μm
In the case of m, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is effective. In the emulsion of the present invention, 50% or more of the total projected area is occupied by silver iodobromide or silver iodochloride tabular grains, and the tabular grains preferably have the (111) plane as a main surface. Here, the tabular silver halide grains are a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship. When viewed from above, the tabular grains have a triangular, quadrangular, hexagonal or rounded shape with these corners removed, and the triangular ones are triangular or square. Those having a square shape, hexagonal shapes having a hexagonal shape, and circular shapes having a circular parallel outer surface.

In the emulsion of the present invention, preferably 50% or more of the total projected area is occupied by tabular grains having a thickness of 0.5 μm or less, and preferably the tabular grains have a circle equivalent diameter of 1.0 μm or more. The equivalent circle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.
The projected area of the particle measures the area on the electron micrograph,
It is obtained by correcting the photographing magnification. The thickness of the particles is easily obtained by evaporating a metal from the oblique direction of the particles together with the reference latex, measuring the shadow length on an electron microscope, and calculating with reference to the shadow length of the latex. Can be

The equivalent circle diameter of the tabular grains of the present invention is preferably at least 1.0 μm, more preferably at least 1.5 μm, further preferably at least 2.0 μm, and further preferably at most 10 μm. The thickness of the tabular grains is more preferably 0.1 μm or less, more preferably 0.08 μm or less, further preferably 0.06 μm or less, and further preferably 0.01 μm or more. The variation coefficient of the equivalent circle diameter in all grains of the emulsion of the present invention is preferably 40% or less, more preferably 25% or less.
%, More preferably 15% or less.

The tabular grains of the present invention are silver iodobromide or silver iodochlorobromide. Other silver salts, for example, rodan silver, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide.

The preferred range of the silver iodide content of the emulsion grains of the present invention is 0.1 to 20 mol%, more preferably 0.3 to 15 mol%, and particularly preferably 1 to 10 mol%. Can be appropriately selected according to the purpose. If it exceeds 20 mol%, the developing speed is generally slow, which is not preferable. The preferred range of the silver chloride content of the tabular grains of the present invention is from 0 to 20 mol%, more preferably from 0 to 15 mol%, and particularly preferably from 1 to 7 mol%. Can be.

Next, the features of the photographic material using the present invention will be described. In a silver halide tabular grain having a thickness of 0.1 μm or less, incident light is strongly reflected by interference, and effective light absorption cannot be obtained. In the present invention, the titanium oxide fine particles are dispersed in a hydrophilic binder such as gelatin constituting an emulsion layer, and the refractive index of the hydrophilic binder is increased while maintaining transparency, whereby reflection at the interface between the tabular grains and the hydrophilic binder is achieved. Light can be reduced.

The silver halide photographic emulsion and silver halide color photographic light-sensitive material of the present invention obtained by dispersing a metal oxide in an emulsion layer containing tabular silver halide grains having a thickness of 0.1 μm or less have a light scattering property. It is not intended to reduce light interference but mainly to reduce light interference mainly depending on the thickness of silver halide tabular grains. US Pat.
This is different from the purpose of 007976. Next, the preferred layer constitution of the silver halide photographic light-sensitive material of the present invention will be described.
The photosensitive material of the present invention comprises at least one photosensitive material on a support.
The layers may be provided with a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit color-sensitive layer having color sensitivity to any of blue light, green light and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are provided in this order from the support side.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-photosensitive layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in DE 1121470 or GB
High-sensitivity emulsion layer as described in US Pat.
It is preferred that the two low-sensitivity emulsion layers are arranged so that the sensitivity gradually decreases toward the support. Also, Japanese Patent Application Laid-Open
Nos. 7-112751, 62-200350, 62
As described in JP-A-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

As described in JP-B-55-34943, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in Japanese Patent Application Laid-Open No. 6-106, the blue light-sensitive layer / GL / RL / GH can be arranged in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a lower sensitivity than the middle layer. Further, there is an arrangement in which a silver halide emulsion layer having a low sensitivity is disposed and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even in the case of three layers having different sensitivities,
As described in JP-A-59-202264,
In the same color-sensitive layer, an intermediate emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be provided in this order from the side away from the support. In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat.
Nos. 271, 4705744, and JP-A-62-1604.
No. 48, 63-89850, B
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as L, GL, and RL is disposed adjacent to or adjacent to the main photosensitive layer. There is no limitation on the preferred layer in which the emulsion of the present invention should be contained, but most of the silver halide tabular grains having a grain thickness of 0.1 μm or less constitute a high-speed emulsion layer. It is preferably used for a sensitive green photosensitive layer or a sensitive red photosensitive layer.

Various additives can be used for the silver halide photographic light-sensitive material which can employ the silver halide photographic emulsion of the present invention, depending on the purpose. These additives are described in more detail in RD Item 17643 (December 1978).
), Item 18716 (November 1979), Item 308119 (December 1989) and Item It
em40145 (September 1997),
The relevant locations are summarized below.

Additive Type RD17643 RD18716 RD308119 Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity increasing agent Same as above 3. 3. Spectral sensitizer, page 23-24, page 648, right column-996 right, -998 right Supersensitizer, page 649, right column Brightener 24 pages 998 right 5. 5. Antifoggant page 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6. Light absorber, page 25-26, page 649, right column-1003 left-1003 right, filter dye, page 650, left column, UV absorber 7. Stain inhibitor 25 pages right column 650 left to right column 1002 right Dye image stabilizer page 25 1002 right 9. Hardening agent Page 26 Page 651 Left column 1004 right to 1005 left 10. Binder page 26 Same as above 1003 right to 1004 right 11. Plasticizers, lubricants 27 pages 650 pages right column 1006 left to 1006 right 12. Coating aid, pages 26 to 27 Same as above 1005 left to 1006 left Surfactant 13. Static page 27 Same as above 1006 right to 1007 left Inhibitor 14. Matting agent 1008 left to 1009 left.

Techniques such as layer arrangement and the like, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives, etc. And development processing are described in EP 056596 A1 (October 1993).
And published patents cited therein. The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36-40, 3. Multilayer effect imparting layer: page 62, lines 15-18, 4. Silver halide composition: page 62, lines 21-25, 5. Silver halide crystal habit: page 62, line 26-30, 6. Silver halide grain size: page 62, lines 31-34, 7. Emulsion manufacturing method: page 62, line 35-40, Silver halide grain size distribution: page 62, 41-42
Row, 9. 9. Tabular grains: page 62, lines 43-46, 10. Internal structure of particle: page 62, line 47 to line 53, Emulsion latent image formation type: page 62, line 54-page 63, 5
Line, 12. 12. Physical ripening and chemical ripening of emulsion: page 63, line 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14-31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49-50, Photographic additives: Research Disclosure (R
D) Item 17643 (December 1978), It
em18716 (November 1979) and Item3
07105 (November 1989). The following shows each item and its related description.

Types of Additives RD17643 RD18716 RD307105 (1) Chemical sensitizer page 23, page 648, right column, page 866 (2) Sensitivity enhancer, page 648, right column (3) Spectral sensitizer, pages 23-24, page 648, right Columns to 866 to 868 Super sensitizer page 649 right column (4) Brightener 24 page 647 page right column 868 (5) Antifoggant, page 24 to 25 page 649 right column 868 to 870 Stabilizer (6) Light absorber, page 25-26, page 649, right column-page 873, filter dye, page 650, left column, UV absorber (7) Stain inhibitor, page 25, right column, 650 left column, right column, page 872 (8) Dye Image stabilizer page 25 page 650 left column page 872 (9) hardener 26 page 651 left column 874-875 (10) binder 26 page 651 left column 873-874 (11) plasticizer, lubricant 27 Page 650 Right column Page 876 (12) Coating aid, 26 to 27 Page 650 Right column 875 to 876 Surfactant (13) Static 27 Page 650 Right column 876 to 877 Inhibitor (14) Matting agent 878-879.

18. Formaldehyde scavenger: 6
Page 4, lines 54-57; Mercapto antifoggant: page 65, line 1-2, 20. Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, line 7-10, 22. General color couplers: p. 65, lines 11-13, 23. Yellow, magenta and cyan couplers: page 65, 1
Lines 4-25, 24. Polymer coupler: page 65, lines 26-28, 25. Diffusible dye-forming coupler: page 65, lines 29-31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39-44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49-53, 30. Other DIR couplers: page 65, line 54-page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34-36.

34. 35. Photosensitive layer thickness and swelling speed: page 66, line 40-page 67, line 1, Back layer: page 67, line 3-8, 36. General processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12-30, 38. Developer additives: page 67, lines 31-44, 39. Inversion processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57-page 68, line 12, 41. Developing time: page 68, lines 13-15, 42. Bleaching-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32-40, 44. Rinsing, rinsing, stabilization: page 69, line 41-page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70, lines 34-38, 48. Use for film with lens: page 70, lines 39-41.

[0083]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.
However, the present invention is not limited to these examples. Example 1 Water was added to 0.18 g of low molecular weight gelatin,
Dissolve and stir at 40 ° C. to obtain a 14% by mass gelatin solution.
The volume was 25 mL. Water (37.7 g) was added to 2.34 g of a commercially available titanium oxide sol TSK-5 (rutile crystal, manufactured by Ishihara Sangyo Co., Ltd., cumulative average particle size: 68 nm (measured by Nikkiso Microtrac UPA)) to obtain an upper liquid. The mass% of the low molecular weight gelatin based on titanium oxide was 25%. Water was added to 2.0 g of non-low molecular weight gelatin and dissolved and stirred at 40 ° C. to obtain 14.3 g of gelatin solution, which was used as a second solution. When the instep solution was added to the second solution, it was confirmed that a uniform gelatin dispersion having no cohesiveness was obtained. TSK-5
Was freeze-dried, and the surface treatment components other than titanium oxide were confirmed by fluorescent X-ray analysis. The result was 11% by mass of silica treatment. On the other hand, zirconia and alumina were 1% by mass or less. When the pH of the water-soluble polymer dispersion was measured, it was 5.5. The difference between this pH value and the literature value of the isoelectric point of titanium oxide (rutile crystal) (“Titanium oxide physical properties and applied technology (Gihodo Publishing)”) 5.6 is 0.1
Met.

Comparative Example 1 Commercially available titanium oxide sol TSK
-5 (rutile crystal, manufactured by Ishihara Sangyo, cumulative average particle size 68n
m (measured by Nikkiso Microtrac UPA) 2.34 g
37.7 g of water was added to the mixture, and 1.25 mL of water was further added without adding low molecular weight gelatin to obtain an upper solution. The mass% of low molecular weight gelatin relative to titanium oxide was 0%. Water was added to 2.2 g of non-low molecular weight gelatin, and the mixture was dissolved and stirred at 40 ° C. to obtain 14.3 g of a gelatin solution, which was used as a second solution. When the instep fluid was added to the second solution, severe aggregation occurred.

Example 2 0.15 g of low molecular weight gelatin
Was added thereto, and the mixture was dissolved and stirred at 40 ° C. to make 1.02 mL of a 14% by mass gelatin solution. Commercially available titanium oxide sol (anatase type crystal, manufactured by CI Kasei, cumulative average particle size 3
Water (28.8) to 3.9 g of 0 nm (manufacturer's catalog value)
g was added to obtain an instep fluid. The mass of low molecular weight gelatin relative to titanium oxide was 25%. Water was added to 1.6 g of non-low molecular weight gelatin and dissolved and stirred at 40 ° C. to obtain 11.7 g of gelatin solution, which was used as a second solution. When the instep solution was added to the second solution, it was confirmed that a uniform gelatin dispersion having no cohesiveness was obtained. When the titanium oxide sol was freeze-dried and surface treatment components other than titanium oxide were confirmed by X-ray fluorescence analysis, the total amount of the other constituent materials was 1% by mass or less when the mass of titanium oxide was 100. When the pH of the water-soluble polymer dispersion was measured, it was 5.5. The difference between the value of the present pH and the literature value of isoelectric point of titanium oxide (anatase type crystal) (“Titanium oxide physical properties and applied technology (Gihodo Publishing)”) 6.1 was 0.6.

Comparative Example 2 Commercially available titanium oxide sol (anatase type crystal, manufactured by C-I-Kasei, cumulative average particle size 30 nm)
(Manufacturer's catalog value) 28.8 g of water was added to 3.9 g, and water was further added to 1.02 m without adding low molecular weight gelatin.
L was added to obtain an instep fluid. The mass% of low molecular weight gelatin relative to titanium oxide was 0%. Water was added to 1.8 g of non-low molecular weight gelatin, dissolved and stirred at 40 ° C. to obtain 11.7 g of gelatin solution, which was used as a second solution. When the instep fluid was added to the second solution, severe aggregation occurred.

Example 3 0.15 g of low molecular weight gelatin
Was added to the mixture, and the mixture was dissolved and stirred at 40 ° C. to make 1.01 mL of a 14% by mass gelatin solution. Commercially available 15% by mass alumina sol (cumulative average particle size 30 nm (manufacturer catalog value))
32.2 g of water was added to 3.6 g to prepare an instep solution. The mass of the low molecular weight gelatin based on aluminum oxide was 25%. Water is usually added to 1.8 g of gelatin having a molecular weight and dissolved and stirred at 40 ° C. to obtain 13.0 g of a gelatin solution.
This was designated as the second liquid. When the instep solution was added to the second solution and the pH was adjusted to 6.5, it was confirmed that a uniform gelatin dispersion having no cohesiveness was obtained. The difference between the pH value of the water-soluble polymer dispersion and the literature value of isoelectric point of γ-alumina (“Physical properties of titanium oxide and applied technology (Gihodo Shuppan)”) 8.0 was 1.5.

Comparative Example 3 Commercially available 15% by mass alumina sol (cumulative average particle size 30 nm (manufacturer's catalog value))
32.2 g of water was added to 3.6 g, and 1.01 mL of water was further added without adding low-molecular-weight gelatin to obtain an upper solution. The mass% of the low molecular weight gelatin based on the aluminum oxide is 0.
%Met. Water was added to 1.8 g of non-low molecular weight gelatin, and dissolved and stirred at 40 ° C. to obtain 13.0 g of gelatin solution, which was used as a second solution. When the instep fluid was added to the second solution, severe aggregation occurred.

[Example 4] Water was added to 1.7 g of low molecular weight gelatin to 20.4 g, and the mixture was dissolved and stirred at 40 ° C. 21.3 g of water is added to 21.3 g of commercially available titanium oxide sol TSK-5.
After adding and diluting 2.7 g, the mixture was added to a low-molecular-weight gelatin solution and stirred to obtain a solution A. The mass of low molecular weight gelatin relative to titanium oxide was 25%. In addition, a non-low molecular weight gelatin was processed by a high-speed jetting device described in JP-A-2000-032487 to prepare a 12.1% by mass solution of gelatin in which the high molecular weight component was reduced, and 29.1 g of the solution was diluted with water. 3 g was dissolved and stirred at 40 ° C. to obtain a second solution. When the instep solution was added to the second solution, it was confirmed that a uniform gelatin dispersion having no cohesiveness was obtained.

When this dispersion was applied on a TAC base (Fuji Tack TD80UF) using a bar coater,
A transparent and smooth film was obtained.

(Application to Silver Halide Photosensitive Material) [Comparative Example 4] A silver halide emulsion Em-A was prepared by the following method.
Was prepared from Em-O. (Preparation of Em-A) 1200 mL of an aqueous solution containing 1.0 g of low molecular weight oxidized gelatin having a weight average molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously.
30 mL of an aqueous solution containing 1.9 g of AgNO ₃ and 30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low molecular weight oxidized gelatin having a weight average molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. Was. At this time, the excess concentration of KBr was kept constant. 6 g of KBr
The mixture was added and heated to 75 ° C. for aging. After ripening, 35 g of succinated gelatin was added. The pH was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and KBr
The aqueous solution was added by the double jet method over 16 minutes.
At this time, the silver potential was set to -40 mV with respect to the saturated calomel electrode.
Kept. Further, an aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method at a flow rate acceleration of 1.2 times the initial flow rate over a period of 15 minutes. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at -40 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. KB so that the potential at the end of the addition becomes -20 mV.
The addition of the r aqueous solution was adjusted. After the temperature was adjusted to 40 ° C., 5.6 g of Compound 1 in terms of KI was added, and 64 mL of a 0.8 M aqueous sodium sulfite solution was further added. Further N
The pH was raised to 9.0 by adding an aqueous solution of aOH and held for 4 minutes to rapidly generate iodide ions.
Returned to 5. After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After completion of the addition, an aqueous solution 250 containing 70 g of AgNO ₃
mL and KBr aqueous solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, yellow blood salt was added in an amount of 1.0 × 10 ⁻⁵ mol per mol of silver. After washing with water,
80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the pH was adjusted to 5.8 and the pAg was adjusted to 8.7 at 40 ° C.

[0093]

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The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively.

The temperature of the above emulsion was raised to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added in terms of Ag, and shelled. Next, sensitizing dyes 1, 2,
3. in the form of a fine solid dispersion,
85 × 10 ⁻⁴ mol, 3.06 × 10 ⁻⁴ mol, 9.0
0 × 10 ⁻⁶ mol was added. Solid fine dispersions of sensitizing dyes 1, 2, and 3 were prepared as follows. As shown in the preparation conditions in Table 1, after dissolving the inorganic salt in ion-exchanged water,
The sensitizing dye was added and dispersed at 2,000 rpm for 20 minutes using a dissolver blade at 60 ° C. to obtain fine solid dispersions of sensitizing dyes 1, 2, and 3. When the sensitizing dye is added and the adsorption of the sensitizing dye reaches 90% of the adsorption amount in the equilibrium state, the calcium nitrate is reduced to a calcium concentration of 250%.
ppm was added. The amount of sensitizing dye adsorbed is determined by separating the solid and liquid layers by centrifugation and measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant, and The amount of dye was determined. After the addition of calcium nitrate,
Potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea and Compound 4 were added to optimize chemical sensitization. N, N- ヂ methylselenourea was added in an amount of 3.40 × 10 ⁻⁶ mol per mol of silver. At the end of the chemical sensitization, Compound 2 and Compound 3 were added to prepare Em-A.

[0096]

[Table 1]

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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In Em-A, particles having an equivalent circle diameter of 1.0 μm or more and a thickness of 0.01 μm or more and 0.1 μm or less occupy 80% (number). Silver iodobromide having an average equivalent sphere diameter of 0.92 μm, an average equivalent circle diameter of 1.2, and an average aspect ratio of 14 (silver iodide content: 4 mol%, silver chloride content: 0%).

(Preparation of Em-B) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 5 g, and the succinated gelatin was trimellitized to a weight average molecular weight of 100,000 containing 35 μmol methionine per gram. The compound 1 was replaced with 8.0 g of compound 6 in terms of KI, and the amount of the sensitizing dye added before the chemical sensitization was changed with respect to the sensitizing dyes 1, 2, and 3. 6.50 × 10 ^-4 mol, 3.40 × 10 respectively
Em- except that the amount was changed to ^-4 mol and 1.00 × 10 ⁻⁵ mol, and the amount of N, N- ヂ methylselenourea added during chemical sensitization was changed to 4.00 × 10 ⁻⁶ mol. Em-B was prepared in the same manner as in A.

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(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g, and the succinated gelatin was converted to a phthalated phthalate having a weight average molecular weight of 100,000 containing 35 μmol methionine per gram. Rate 9
7 g of phthalated gelatin, compound 1 was replaced by 7.1 g of compound 7 in terms of KI, and the amount of sensitizing dye added before chemical sensitization was 7 .80 × 10 ⁻⁴ mol, 4.08 × 10 ⁻⁴ mol,
1.20 × 10 ⁻⁵ mol and the amount of N, N- 量 methylselenourea added during chemical sensitization was 5.00 ×
Except for changing to 10 ⁻⁶ mol, E
mC was prepared.

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(Adjustment of Em-E) Weight average molecular weight 150
1.0 g of low molecular weight gelatin and 1.0 g of KBr
The aqueous solution containing 1200 mL was kept at 35 ° C. and stirred vigorously. 30 mL of an aqueous solution containing 1.9 g of AgNO ₃ , KB
30 mL of an aqueous solution containing 1.5 g of r and 0.7 g of low-molecular-weight gelatin having a weight-average molecular weight of 15,000 was added over 30 seconds by a double jet method to form nuclei. At this time,
The excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 15 g of succinated gelatin and 20 g of the above-mentioned trimellitated gelatin were added. The pH was adjusted to 5.5. AgNO
150 mL of an aqueous solution containing 30 g of No. ₃ and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method at a flow rate acceleration of 1.2 times the initial flow rate over a period of 15 minutes. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at −25 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. KB so that the potential at the end of the addition becomes -20 mV.
The addition of the r aqueous solution was adjusted. KBr was added and the potential was-
After the voltage was adjusted to 60 mV, 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was added. After the addition, an aqueous solution of low molecular weight gelatin having a weight average molecular weight of 15,000 and AgN
AgI fine particles having an equivalent sphere diameter of 0.008 μm prepared by mixing an O ₃ aqueous solution and a KI aqueous solution in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570 and immediately before the addition. 7. Emulsion was converted to KI.
While continuously adding 0 g, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes while keeping the potential at −60 mV. At this time, yellow blood salt was added in an amount of 1.0 × 10 ⁻⁵ mol per mol of silver. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the pH and pAg were adjusted to 5.8 and 5.8 at 40 ° C.
Adjusted to 7.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively. Sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the added amount was 7.73 ×
10 ⁻⁴ mol, 1.65 × 10 ⁻⁴ mol, 6.20 × 1
0 except that the ^-5 mol performs chemical sensitization in the same manner as Em-A, was prepared Em-E.

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[0112]

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[0113]

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(Preparation of Em-F) Weight average molecular weight 150
1.0 g of low molecular weight gelatin and KBr of 1.00.
1200 mL of an aqueous solution containing 0 g was kept at 35 ° C. and stirred vigorously. 30 mL of an aqueous solution containing 1.9 g of AgNO ₃ ,
30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low-molecular-weight gelatin having a weight-average molecular weight of 15,000 was added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 5 g of KBr
The mixture was added, heated to 75 ° C. and aged. After aging, 20 g of succinated gelatin and 15 g of phthalated gelatin were added. The pH was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Furthermore, AgNO
Aqueous solution containing 110 g of No. ₃ and KBr aqueous solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was prepared with a silver iodide content of 3.
At the same time, the flow rate was increased to 8%, and the silver potential was kept at -25 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. After adjusting the potential to −60 mV by adding an aqueous KBr solution, 9.2 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and K
An aqueous Br solution was added over a period of 20 minutes while maintaining the potential at 60 mV. At this time, yellow blood salt was added in an amount of 1. mol per mol of silver.
0 × 10 ⁻⁵ mol was added. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added,
The pH and the pAg were adjusted to 5.8 and 8.7, respectively. The calcium, magnesium and strontium contents of the above emulsion were measured by ICP emission spectroscopy.
They were 15 ppm, 2 ppm and 1 ppm, respectively. Sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6, and the added amount was 8.50 × 10 ⁻⁴ mol and 1.8, respectively.
Em-F was prepared by performing chemical sensitization in the same manner as in Em-B except that the amounts were 2 × 10 ⁻⁴ mol and 6.82 × 10 ⁻⁵ mol.

(Preparation of Em-G) Weight average molecular weight 150
1.0 g of low molecular weight gelatin of 00 and 1.0 g of KBr
Was kept at 35 ° C. and stirred vigorously. AgNO ₃ chemical sensitization is an aqueous solution 3 containing 1.9 g
0 mL, KBr 1.5 g and weight average molecular weight 15,000
30 g of an aqueous solution containing 0.7 g of low-molecular-weight gelatin was added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. KBr
Was added, and the mixture was heated to 75 ° C. and aged. After the ripening, 15 g of the above-mentioned trimellitized gelatin and 20 g of the above-mentioned phthalated gelatin were added. The pH was adjusted to 5.5. 150 mL of aqueous solution containing 30 g of AgNO ₃ and KB
The r aqueous solution was added over 16 minutes by the double jet method. At this time, the silver potential is set to −25 with respect to the saturated calomel electrode.
mV. Further, an aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method at a flow rate acceleration of 1.2 times the initial flow rate over a period of 15 minutes. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at −25 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential became -60 mV. 7.1 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition was completed, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 the potassium ferrocyanide per silver mole ^{- 5} moles was added. After washing with water, 80 g of lime-treated gelatin having a calcium concentration of 1 ppm was added, and
At 0 ° C., the pH was adjusted to 5.8 and the pAg to 8.7. The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy, which was 15 ppm, 2 ppm and 1 ppm, respectively. Sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the added amount of each was 1.00 × 10 ⁻³ mol, and 2.
Em-G was prepared by performing chemical sensitization in the same manner as in Em-C except that the amount was changed to 15 × 10 ⁻⁴ mol and 8.06 × 10 ⁻⁵ mol.

(Preparation of Em-J) In the preparation of Em-B, sensitizing dyes added before chemical sensitization were changed to sensitizing dyes 7 and 8, and the added amount of each was 7.65 × 10 ^−4. Mole,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

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[0120]

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(Preparation of Em-L) (Preparation of Silver Bromide Emulsion) Average sphere equivalent diameter: 0.6 μm, average aspect ratio: 9.0, silver: 1.16 per kg of emulsion
A silver bromide tabular emulsion containing 66 g of mol and gelatin was prepared. (Growth Step 1) 0.3 g of modified silicone oil was added to 1250 g of an aqueous solution containing 1.2 g of potassium bromide and succinated gelatin having a succination ratio of 98%. After the silver bromide tabular emulsion containing 0.086 mol of silver was added, the mixture was stirred at 78 ° C. An aqueous solution containing 18.1 g of silver nitrate and 5.4 mol of silver to which silver iodide fine particles having an equivalent sphere diameter of 0.037 μm were added were added. Further, at this time, the pAg of the aqueous potassium bromide solution was 8.times.
It was added while adjusting to be 1.

(Growth Process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt and 2.5 mg of thiourea dioxide were added. Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous potassium bromide solution were added over 66 minutes while accelerating with a double jet. At this time, silver iodide fine particles having an equivalent sphere diameter of 0.037 μm were added in an amount of 7.0 mol based on silver to be added. At this time, the pAg is 8.
The amount of potassium bromide in the double jet was adjusted so as to be 1. After the addition was completed, 2 mg of sodium benzenethiosulfonate was added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous solution of potassium bromide were added by a double jet over 16 minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9. (Addition of poorly soluble silver halide emulsion 4) After adjusting the above host grains to 9.3 with an aqueous potassium bromide solution, 25 g of the above silver iodide fine grain emulsion having an equivalent sphere diameter of 0.037 μm was added within 20 seconds. Was added rapidly. (Formation 5 of outermost shell layer) An aqueous solution containing 34.9 g of silver nitrate was further added over 22 minutes.

This emulsion was tabular grains having an average aspect ratio of 9.8 and an average equivalent sphere diameter of 1.4 μm, and had an average silver iodide content of 5.5 mol%.

(Chemical sensitization) After washing with water, the succinization ratio was 98.
% Succinated gelatin and calcium nitrate at 40 ° C
PH, adjusted to 5.8, pAg, 8.7. The temperature was raised to 60 ° C., the silver bromide fine grain emulsion of 0.07 .mu.m 5 × 10 ^-3
After 20 minutes, sensitizing dyes 9, 10, and 11 were added. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, and compound 4 were added, and the mixture was optimally chemically sensitized. Compound 3 was added 20 minutes before the end of the chemical sensitization, and Compound 5 was added at the end of the chemical sensitization. Here, the optimal chemical sensitization is 1/100.
Means that the sensitizing dye and each compound were selected from the added amount range of 10 ^-1 to 10 ^-8 mol per mol of silver halide so that the sensitivity at the time of exposure was maximized.

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[0127]

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(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was charged into a reaction vessel equipped with a stirrer, and the temperature of the solution was maintained at 70 ° C. To this solution, 276 mL of an aqueous solution of AgNO ₃ (containing 12.0 g of AgNO ₃ ) and an aqueous solution of KBr having an equimolar concentration were added over 7 minutes by a controlled double jet addition method while maintaining the pAg at 7.26. Then, the temperature was lowered to 68 ° C., and 7.6 mL of 0.05% by mass thiourea dioxide was added. Subsequently, 592.9 mL of an AgNO ₃ aqueous solution (including 108.0 g of AgNO ₃ )
A mixed aqueous solution of KBr and KI having an equimolar concentration with (KI is 2.
(0 mol%) was added by a controlled double jet addition method over 18 minutes and 30 seconds while maintaining the pAg at 7.30. Five minutes before the end of the addition, 18.0 mL of 0.1% by mass thiosulfonic acid was added.

The obtained particles had an average sphere equivalent diameter of 0.19 μm.
m, cubic grains having an average silver iodide content of 1.8 mol%.
Was. Em-O is desalted by ordinary flocculation method
-After re-dispersing by washing with water, the pH is adjusted to 6.degree.
2. The pAg was adjusted to 7.6. Next, on Em-O
Then, the following spectral sensitization and chemical sensitization were performed. Destination
Sensitizing dyes 10, 11 and 12 per mole of silver
3.37 × 10 each ^-4Mol / mol, KBr 8.82
× 10^-4Mol / mol, sodium thiosulfate 8.83
× 10^-5Mol / mol, potassium thiocyanate is 5.9
5 × 10^-4Mol / mol and potassium chloroaurate.
07 × 10^-5Aged at 68 ° C with mol / mol added
Was. The aging time is the highest sensitivity for 1/100 second exposure.
It was adjusted to be.

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For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. Further, according to the examples of JP-A-3-237450, gold sensitization was carried out in the presence of the spectral sensitizing dyes shown in Table 2 and sodium thiocyanate.
Sulfur sensitization and selenium sensitization are applied. Emulsions D and H,
I and K contain optimum amounts of Ir and Fe. Emulsion M, N
Is subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

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[Table 2]

[0135]

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[0136]

[Table 3]

In Table 3, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

1) Support The support used in this example was prepared by the following method.

1) First layer and undercoat layer For a polyethylene naphthalate (PEN) support having a thickness of 90 μm, the processing atmosphere pressure was applied to both surfaces of each support.
66 × 10 Pa, H ₂ O partial pressure in atmosphere gas 75%, discharge frequency 30 kHz, output 2500 W, processing intensity 0.5
Glow discharge treatment was performed at kV · A · min / m ² . On this support, a coating solution having the following composition was applied as a first layer for forming a back layer at a coating amount of 5 mL / m ² by using a bar coating method described in JP-B-58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass Poly (degree of polymerization 20) oxyethylene 0.1 parts by mass Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, heat-treated at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, heat-treated, and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² by using a bar coating method.

Gelatin 1.01 part by mass Salicylic acid 0.30 part by mass Resorcin 0.40 part by mass Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 part by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n -Propanol 10.08 parts by mass Further, a second layer and a third layer described later are sequentially applied on the first layer, and finally, a color negative photosensitive material having a composition described later is overlaid on the opposite side across the support. Thus, a transparent magnetic recording medium having a silver halide emulsion layer was prepared.

2) Second layer (transparent magnetic recording layer) (i) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ^{2 /} g, Hc: 6.56 × 10 ⁴ A
/ M, σs: 77.1 Am ² / kg, σr: 37.4 A
m ² / kg) 1100 parts by mass, water 220 parts by mass and a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] 165
A part by weight was added and kneaded well with an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Further, the mixture was kneaded again in an open kneader for 4 hours according to the following formulation.

The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the mixture was finely dispersed in a sand mill (1/4 G sand mill) at 2000 rpm for 4 hours according to the following formulation. did. As the medium, glass beads having a diameter of 1 mm were used.

The kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

(Ii) Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g These are mixed. After that, the mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid". An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation.

(A) Sumicorundum AA-1.5 (average primary particle diameter 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetylcellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ceramic-coated sand mill (1/1)
(4G sand mill) at 800 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used. (B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used.

This is a dispersion of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and has a solid content of 30%.

(Iii) Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK -ST "[dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g (solid content 20%, dilution Solvent: methyl ethyl ketone / cyclohexanone = 1/1) 170 g of methyl ethyl ketone 170 g of cyclohexanone The coating solution obtained by mixing and stirring the above was applied by a wire bar so as to have an application amount of 29.3 mL / m ² . Drying is 1
Performed at 10 ° C. The thickness as a magnetic layer after drying is 1.0
μm.

3) Third layer (layer containing higher fatty acid ester slip agent) (i) Preparation of stock solution of slip agent The following solution A was heated and dissolved at 100 ° C, added to Solution A, and dispersed with a high-pressure homogenizer. To prepare a stock solution of a slip agent. A liquid following compounds 399 parts by weight _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 50 H 101 The following compound 171 parts by weight _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H Cyclohexanone 830 parts by weight.

Liquid A Cyclohexanone 8600 parts by mass (ii) Preparation of spherical inorganic particle dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by mass Compound 8 2.93 parts by mass

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88.00 parts by mass of Sea Hosta KEP50 (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).

After stirring for 10 minutes with the above formulation, the following is further added. 252.93 parts by mass of diacetone alcohol While cooling the above liquid with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

(Iii) Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.

XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass methyl ethyl ketone 120 parts by mass cyclohexanone 120 parts by mass (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone) = 1/1) While cooling with ice and stirring, the ultrasonic homogenizer “SONI
The dispersion was performed for 2 hours using FIER450 (manufactured by BRANSON Corporation) to complete a spherical organic polymer particle dispersion c2.

(Iv) Preparation of Coating Solution for Third Layer A coating solution for a third layer was prepared by adding the following to 542 g of the stock solution for dispersing slip agent.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion liquid [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion liquid [c2] 300 g FC431 2.65 g (3M Corporation) BYK310 5.3 g (manufactured by BYK Chemi Japan KK, solid content 25%).

The above third layer coating solution was applied on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a color negative film.

(Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: Gelatin hardener (specific compounds are described below with numerical values following symbols and chemical formulas after). The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExM-1 0.066 ExC-1 0.002 ExC -3 0.002 Cpd-2 0.001 F-8 0.010 HBS-1 0.005 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 F-8 0.012 Solid disperse dye ExF-7 0.120 HBS-1 0.074.

Third layer (intermediate layer) ExC-2 0.050 Cpd-1 0.090 Polyethyl acrylate latex 0.200 HBS-1 0.100 Gelatin 0.700 Fourth layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-4 0.121 ExC-5 0.010 ExC-6 0.007 ExC-8 0.050 ExC-9 0.020 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.114 HBS-5 0.038 Gelatin 1.474.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 ExC-8 0.016 ExC-9 0.005 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.129 Gelatin 1.086 6th Layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 ExC-8 0.110 ExC-9 0.020 Cpd-20 0.064 Cpd-4 0.077 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245.

Seventh layer (intermediate layer) Cpd-1 0.094 Cpd-6 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886 Eighth Layer (layer giving a multilayer effect to the red sensitive layer) Em-J silver 0.293 Em-K silver 0.293 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExM-4 0.026 ExY-1 0.016 ExY-4 0.036 ExC-7 0.026 HBS-1 0.090 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 ExC-7 0.007 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.470 10th layer (medium sensitivity green) Sensitive emulsion layer) Em-F silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-3 0.007 ExC-6 0.010 ExC-7 0.012 ExC-8 0.010 HBS-1 0.065 HBS-3 0.002 HBS-5 0.020 Cpd-5 0.004 Gelatin 0.446.

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Em-E Silver 0.794 ExC-6 0.002 ExC-8 0.010 ExM-1 0.013 ExM-2 0.011 ExM-30 030 ExM-4 0.017 ExY-3 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.939 12th layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.150 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-6 0.010 HBS-1 049 Gelatin 0.630 13th layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.24 0 ExC-1 0.027 ExC-7 0.013 ExY-1 0.002 ExY-2 0.890 ExY-4 0.058 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS -5 0.074 gelatin 2.058.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.714 ExY-2 0.211 ExY-4 0.068 Cpd-2 0.075 Cpd-3 0.001 HBS-10 071 Gelatin 0.678 Fifteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 026 F-18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 Gelatin 1.984 16th layer (second protective layer) H-1 0.400 B-1 (diameter 1 0.750 μm) 0.050 B-2 (diameter 1.7 μm) 0.150 B-3 0.050 S-1 0.200 gelatin 0.750 Further, the storage stability, processing property, pressure resistance, and protection of each layer are appropriately determined. mold·
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-6, B-4 to B-6, F-1 to F
-17 and a lead salt, a platinum salt, an iridium salt, and a rhodium salt.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the twelfth layer was dispersed by the following method.

ExF-2 wet cake (containing 17.6 mass% water) 2.800 kg sodium octylphenyldiethoxymethanesulfonate (31 mass% aqueous solution) 0.376 kg F-15 (7% aqueous solution) 011 kg Water 4.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH) After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, the peripheral speed was 10 m / min using an agitator mill LMK-4.
s, a discharge rate of 0.6 kg / min, a filling rate of zirconia beads having a diameter of 0.3 mm of 80%, and an absorbance ratio of the dispersion of 0.29.
To obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-7
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.
The compounds used for each layer are shown below.

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The above silver halide color photographic light-sensitive material is referred to as Sample 001. Sample 001 was exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd.
Remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-3
No. 60B is equipped with the evaporation correction means described in Publication Technique No. 94-4992 (issued by the Invention Association). The processing steps and the composition of the processing solution are shown below.

(Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C ─ 5L fixing ( 2) 50 seconds 38.0 ℃ 8 mL 5L water washing 30 seconds 38.0 ℃ 17 mL 3L stable (1) 20 seconds 38.0 ℃ ─ 3L stable (2) 20 seconds 38.0 ℃ 15 mL 3L drying 1 minute 30 seconds 60.0 ℃ * replenishment amount Is per 35 mm width and 1.1 m width of photosensitive material (equivalent to one shot per 24 shots).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above-mentioned processing machine is 10
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² . The composition of the treatment liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy-6 Methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate Salt 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenisher (g) 1,3-diaminopropanetetraacetic acid ferric ammonium ammonium monohydrate 113 170 ammonium bromide 70 105 ammonium nitrate 14 21 succinic acid 34 51 maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with ammonia water] 4.6 4.0.

(Fixing (1) tank liquid) A mixture of the bleaching tank liquid and the following fixing tank liquid in a ratio of 5 to 95 (volume ratio).

(PH 6.8) (Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0L 1.0L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45 (Washing water) Tap water is replaced with H-type strongly acidic cation exchange resin (Rohm and Haas Co.) Amberlite IR-120B)
And water through a mixed-bed column filled with an OH-type strongly basic anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by isocyanuric dichloride Sodium acid 2
0 mg / L and 150 mg / L sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization: 10) Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

Example 5 In comparison with Comparative Example 4, only the sixth layer (high-sensitivity red-sensitive emulsion layer) was changed as follows, and the other components were the same and the same processing was performed.

Em-A Silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 ExC-8 0.110 ExC-9 0.020 Cpd-2 0.064 Cpd-40 0.077 HBS-1 0.329 HBS-2 0.120 Gelatin 1.000 Titanium oxide 0.731 g Here, titanium oxide is a low molecular weight gelatin dispersion of TSK-5 (including 0.180 g of low molecular weight gelatin), and the remaining The emulsion was dissolved to form a gelatin dispersion (containing 0.820 g of non-low molecular weight gelatin), which was added thereto. At the time of addition, the solution pH was adjusted to 11, and after adjusting the coating solution, the pH was readjusted to 6. In Example 5, the sharpness of red was significantly increased as compared with Comparative Example 4, and the sensitivity was increased, but the granularity was not changed.

Example 6, Comparative Example 6 (Mass ratio of low-molecular-weight gelatin to metal oxide fine particles) In Example 2, except that the masses of the low-molecular-weight gelatin solution and the non-low-molecular-weight gelatin solution were as follows: Liquid preparation was performed in the same manner.

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As a result, in Examples 6A and 6B, a coatable and transparent film could be prepared. Example 6
Although C was difficult to dry, a transparent film could be prepared after drying. On the other hand, in Comparative Example 6D, the viscosity was significantly reduced,
Application was not possible.

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As described above, according to the water-soluble polymer dispersion of the present invention, the function of fine particles can be exhibited even when the pH is significantly restricted. It is suitably used for certain gelatins.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03C 1/035 G03C 1/035 HGBL 1/047 1/047 1/06 1/06 502 502 7/26 7 / 26 // B01J 13/00 B01J 13/00 CF term (reference) 2H016 BB01 BB02 BB04 BD00 BJ00 2H023 BA02 BA03 BA04 CD00 CE00 DB00 DB05 4G065 AA01 AA06 AB19X BA07 BA13 BB01 BB02 CA13 DA09 EA03 EA06 4J002 AD01 DA011 DE146 FA086 FB076 GP03 HA06

Claims (15)

[Claims] 1. A water-soluble polymer dispersion in which metal oxide fine particles having a cumulative average particle diameter of 1 to 100 nm are uniformly dispersed, and low molecular weight gelatin contains 0.001% to 200% of the total mass of the metal oxide fine particles. 2. The water-soluble polymer dispersion according to claim 1, wherein the pH is from 5.0 to 7.0. 3. The composition of a metal oxide fine particle having a composition of 75 to
100% by mass is occupied by metal oxides having an isoelectric point whose difference from the pH value of the water-soluble polymer dispersion is -2.0 to 2.0. Item 3. The water-soluble polymer dispersion according to Item 1 or 2. 4. The water-soluble polymer dispersion of metal oxide fine particles according to claim 1, wherein the water-soluble polymer contains non-low molecular weight gelatin. 5. The non-low molecular weight gelatin according to claim 4, wherein a high molecular weight component having a molecular weight of about 2,000,000 or more is in a range of 3% or less in a molecular weight distribution measured according to the PAGI method. Water-soluble polymer dispersion. 6. The water-soluble polymer dispersion according to claim 1, wherein the low molecular weight gelatin is chemically modified. 7. The water-soluble polymer dispersion according to claim 1, wherein the metal oxide is at least one selected from the group consisting of titanium oxide and zirconium oxide. 8. A method according to claim 1, wherein at least a part of the metal oxide fine particles is surface-treated, and 60% by mass or more of the total amount of the surface-treated substance is an oxide of the same kind. The water-soluble polymer dispersion according to any one of the above. 9. The method according to claim 8, wherein at least a part of the metal oxide fine particles is surface-treated, and 80% by mass or more of the total amount of the surface-treated substance is an oxide of the same type. Water-soluble polymer dispersion of 10. The method according to claim 1, wherein at least a part of the metal oxide fine particles is surface-treated, and the total amount of the surface-treated substance is 2% or less of the total mass of the fine particles. Item 10. A metal oxide fine particle water-soluble polymer dispersion according to item 8. 11. A solid composition obtained by drying the water-soluble polymer dispersion according to any one of claims 1 to 10. 12. A dispersion containing the water-soluble polymer dispersion according to any one of claims 1 to 10, wherein the coefficient of variation of the equivalent circle diameter of all silver halide grains is 40% or less, and the total projected area is A silver halide photographic emulsion characterized in that at least 50% is occupied by silver halide tabular grains satisfying the following (i) and (ii). (I) Tabular silver iodobromide or silver iodochlorobromide grains having a (111) plane as a main surface. (Ii) A circle equivalent diameter of 1.0 μm or more and a thickness of 0.01 μm or more and 0.1 μm or less. 13. The silver halide photographic emulsion according to claim 12, wherein the coefficient of variation is 25% or less. 14. The silver halide photographic emulsion according to claim 13, wherein the coefficient of variation is 15% or less. 15. A silver halide photographic material having at least one layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support, A silver halide photographic material comprising the silver halide photographic emulsion according to any one of claims 12 to 14 in at least one of the silver halide emulsion layers.