JP2001281780A - Photosensitive silver halide emulsion and silver halide photographic sensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive silver halide emulsion having high sensitivity and excellent in graininess, preservability and aptitude for production and a silver halide photographic sensitive material containing the emulsion. SOLUTION: In the photosensitive silver halide emulsion containing silver halide grains, gelatin including 5-30% high molecular weight component whose molecular weight is about >=2,000,000 and <=55% low molecular weight component whose molecular weight is about >=100,000 in its molecular weight distribution measured according to the PAGI method is contained. The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer containing the emulsion on the base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light-sensitive silver halide emulsion and a silver halide photographic light-sensitive material containing the emulsion. More specifically, the present invention relates to a photosensitive silver halide emulsion containing gelatin having a controlled molecular weight distribution and having high sensitivity and excellent in graininess, storage stability and production suitability, and a silver halide photographic material containing the emulsion.

[0002]

2. Description of the Related Art In recent years, the demand for photosensitive silver halide emulsions for photography has become increasingly severe, and photographic characteristics such as high sensitivity, image quality such as graininess and sharpness, and further, storage stability,
There is also a higher demand for so-called toughness such as pressure resistance. Further, the silver halide grains of the photosensitive silver halide emulsion tend to agglomerate during the manufacturing process, and this agglomeration causes adverse effects such as softening of photographic characteristics and deterioration of graininess. It is known that this tendency of aggregation is further deteriorated by increasing the size of silver halide grains for high sensitivity or by flattening the grain shape. There is also a desire for improvement.

Conventionally, various studies have been made on the prevention of aggregation of emulsions. For example, Pierre Glafkides, “Ch
imie et Physique Photographiques ”(5th.ed., 1'Usi
ne, Paris, 1987) states that flocculation can be reduced by vigorous stirring, increasing temperature, diluting silver nitrate solution, and increasing gelatin content to a certain limit during grain formation. . However, the demand for the suitability for the production of high-sensitivity silver halide emulsions has been further increased, and in the case of emulsions which have been flattened for high sensitivity, satisfactory results cannot be obtained by conventional techniques.

As another means of improvement, studies have been made to enhance the protective colloidal properties of gelatin. For example, a molecular weight of 9
An octahedral twin emulsion containing gelatin in which less than 25,000 components are 25% or less is disclosed in JP-A-56-85744, which is an octahedron containing a so-called soluble chain-extended gelatin obtained by increasing the molecular weight of gelatin while keeping it soluble. Emulsion is U.S. Pat.
No. 8,889. These techniques were effective for normal crystal emulsions such as octahedral emulsions, but were insufficient for tabular emulsions. Further, Japanese Patent Laid-Open No. 5-1136 discloses a technique for preventing aggregation of a tabular silver halide emulsion containing gelatin containing a high molecular weight component of 12% or more.
JP-A-11-237704 discloses a method for producing a tabular silver halide emulsion produced in the presence of gelatin containing 30% or more of a high molecular weight component having a molecular weight of 280,000 or more. These techniques show some improvement in the prevention of aggregation of tabular emulsions.However, in the case of gelatin having an excessively high molecular weight component, the filterability of the gelatin itself deteriorates, and as a result, the filterability of the emulsion also deteriorates. It has become clear that this creates a new problem of causing

On the other hand, in order to enhance the sensitivity of a silver halide emulsion, (1) the number of photons absorbed by one grain must be increased, and (2) photoelectrons generated by light absorption are converted into silver clusters (latent images). It is necessary to increase the conversion efficiency and (3) to increase the development activity for effectively utilizing the latent image formed. Increasing the size increases the number of absorbed photons per particle, but reduces the image quality. Increasing the developing activity is also an effective means for increasing the sensitivity, but in the case of parallel type development such as color development, graininess is generally accompanied. In order to increase the sensitivity without deterioration in graininess, it is most preferable to increase the efficiency of converting photoelectrons into a latent image, that is, to increase the quantum sensitivity. In order to increase the quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible. It is known that a reduction sensitization method in which small silver nuclei having no development activity are formed inside or on the surface of silver halide is effective for preventing recombination.

The use of reduction sensitization as a means for providing high-sensitivity emulsions has been studied. For example, tabular silver halide emulsions subjected to reduction sensitization are disclosed in JP-A-8-62768.
Nos. 9-1889973 and 10-268456, but there is still room for improvement in terms of storage stability.

[0007]

An object of the present invention is to provide a photosensitive silver halide emulsion having high sensitivity and excellent in graininess, storability and production suitability, and a silver halide photographic light-sensitive material containing the emulsion. That is.

[0008]

Means for Solving the Problems The inventors of the present invention have found that when the emulsion subjected to reduction sensitization contains gelatin of the present invention whose molecular weight distribution is controlled, storage stability such as increase in storage fog and latent image fluctuation is remarkably improved. The present inventors have found that an unexpected effect of improvement can be exhibited, and have completed the present invention. That is, the above object of the present invention could be achieved by the following means.

(1) A photosensitive silver halide emulsion containing silver halide grains, characterized by containing gelatin satisfying the requirement (a).

(A) In the molecular weight distribution of the gelatin measured according to the PAGI method, the high molecular weight component having a molecular weight of about 2,000,000 or more is 5% to 30%, and the molecular weight is about 10% or less.
10,000 or less low molecular weight components are in the range of 55% or less.

(2) The photosensitive silver halide emulsion as described in (1) above, which contains gelatin satisfying the requirement (b).

(B) In the molecular weight distribution of the gelatin measured according to the PAGI method, a high molecular weight component having a molecular weight of about 2,000,000 or more is 5% to 15%, and a molecular weight of about 10% or less.
10,000 or less low molecular weight components are in the range of 50% or less.

(3) The light-sensitive silver halide emulsion as described in (1) or (2) above, which contains gelatin satisfying the requirement (c).

(C) The gelatin is a soluble gelatin crosslinked with a crosslinking agent.

(4) The photosensitive silver halide emulsion as described in any one of (1) to (3) above, which contains gelatin satisfying the requirement (d).

(D) The gelatin is cross-linked using at least one cross-linking agent selected from the group consisting of s-triazine compounds, vinyl sulfone compounds, carbamoyl ammonium salts and carbodiimide compounds as a cross-linking agent. Soluble alkali-treated gelatin.

(5) The light-sensitive silver halide emulsion as described in any one of (1) to (4) above, wherein the emulsion has a hole trap zone in at least one of the inside and the surface of the silver halide grains.

(6) The tabular silver halide grains having an aspect ratio of 8.0 or more occupy 60% or more of the total projected area of the silver halide grains. The photosensitive silver halide emulsion according to any one of the above 1) to 1).

(7) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the light-sensitive silver halide emulsion layer described in the above (1)
A silver halide photographic light-sensitive material comprising the light-sensitive silver halide emulsion according to any one of (6) to (6).

(8) The silver halide photographic material as described in the above item (7), further comprising a magnetic recording layer containing magnetic particles on the back surface opposite to the support.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The gelatin used in the emulsion of the present invention (hereinafter, also referred to as "the gelatin of the present invention") is a collagen tissue whose structure is decomposed by alkali or acid to give water solubility. 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 components of gelatin 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. This method is described in detail in Takashi Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, Journal of the Photographic Society of Japan, Vol. 47, No. 4, 1984, pp. 237-247.

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

(Measurement conditions) Column: Shodex Asahipak GS-620 7G (8 mm ID × 500 mm)
× 2 Guard column: Shodex Asahipak GS-1G 7B Eluent: 0.2 mol / L phosphate buffer (pH
6.8) Flow rate: 0.8 ml / min Column temperature: 50 ° C. Detection: UV 230 nm Sample concentration: 0.5 wt% The GPC curve obtained by taking the retention time on the horizontal axis and the absorbance on the vertical axis The peak of the exclusion limit appears, followed by the peaks of the β component and α component of gelatin, and the shape becomes like a tail as the retention time becomes longer.

In the present invention, the proportion of the high molecular weight component having a molecular weight of about 2,000,000 or more is determined by calculating the proportion of the exclusion limit peak area to the whole area. Specifically, a vertical line is drawn from the minimum point of the GPC curve appearing at the 17th quartile of the retention time to the horizontal axis, and the ratio of the area of the high molecular weight side (high molecular weight component) to the entire area from the vertical line is calculated. calculate. Further, the ratio of the low molecular weight component having a molecular weight of about 100,000 or less is determined by calculating the ratio of the area of the α component or less to the whole area. Specifically, a perpendicular line is drawn from the minimum point of the GPC curve between the β component peak and the α component peak appearing at the 23rd retention time to the horizontal axis, and a portion on the low molecular weight side from the perpendicular line (low molecular weight component) Calculate the ratio of the area of) to the total area.

In the gelatin of the present invention, the high molecular weight component having a molecular weight of about 2,000,000 or more is controlled to 5% to 30%, and the low molecular weight component having a molecular weight of about 100,000 or less is controlled to 55% or less. If the amount of the high molecular weight component exceeds 30%, the filterability rapidly deteriorates, which is not preferable. When the low molecular weight component exceeds 55% and / or the high molecular weight component is 5%
If less than the above, the effect of the present invention is not sufficiently exhibited. In order to exhibit the effects of the present invention, a high molecular weight component having a molecular weight of about 2,000,000 or more has a molecular weight of 5% to 15%,
It is particularly preferred that the low molecular weight component of 10,000 or less is 50% or less.

[0028] The general method for producing gelatin is well known and is described, for example, by TJ James (THJ).
ames), The Theory of the Photographic Proces
s) 4th edition, 1977 (published by Macmillan), p. 55, Handbook of Scientific Photography (above), pp. 72-75 (Maruzen Co., Ltd.), Shinichi Kikuchi, Photochemistry, 1976 (Kyoritsu Shuppan) 213, edited by Shiro Akahori and Saburo Mizushima, Protein Chemistry, 1955 (Kyoritsu Shuppan), page 453.

For example, in the case of alkali-treated gelatin,
After removing calcium from the bone and skin of the raw material, the collagen structure is loosened by immersion in lime, then extracted with warm water, concentrated and dried. In general, extraction is performed with the number of extractions set in 1 to 7 stages, and the extraction temperature increases with the number of extractions.

The method for producing the gelatin of the present invention is roughly classified into the following two methods.

1. Method Not Performing Gelatin Crosslinking For example, the following method is used. Production method In the above-mentioned production method, the gelatin extract at the early stage of the extraction is eliminated by using the gelatin extract at the latter stage of the extraction. Manufacturing method In the above manufacturing method, the processing temperature is set to less than 40 ° C. in the manufacturing steps from extraction to drying. Manufacturing method A gelatin gel is dialyzed against cold water (15 ° C.). [The Journal of Photographic Science (T
he Journal of Photographic Science), vol. 23, p. 33 (1975)]. Production method Fractionation method using isopropyl alcohol.
[Discussions of the Faraday Society, 18
Vol., Page 288 (1954)].

The gelatin of the present invention can be obtained by using the above production methods alone or in combination.

2. Method Using Gelatin Crosslinking Agent As the gelatin used in the present invention, one whose molecular weight distribution is controlled by crosslinking gelatin is more preferably used. There are two cross-linking methods: a method in which gelatin molecules are cross-linked by an enzyme, and a method in which a cross-linking agent is added to form a chemical bond between gelatin molecules to cross-link gelatin molecules.

As a typical method of the enzyme method used in the present invention, gelatin crosslinked with transglutaminase will be described. The transglutaminase enzyme can crosslink gelatin by a function of catalyzing an acyl transfer reaction between a γ-carboxamide group of a glutamine residue of gelatin, which is a protein, and various primary amines. Transglutaminase is derived from animals, plants, and microorganisms.For example, animal-derived ones include mammalian organs such as guinea pig liver, those extracted from blood, and plant-derived ones derived from pea. Extracted and derived from microorganisms are extracted from actinomycetes. In the present invention, any source having transglutaminase activity can be preferably used.

The transglutaminase used in the present invention can be prepared, for example, by the method of Clark et al. (Achives of Biochemistr.
y and Biophysics, 79, 338 (1959)), the method of Connel et al. (J. Bilogical Chemistry, 246 (1971)),
Those synthesized by either the method described in 207149 or the method described in JP-A-6-30770 can be preferably used. These transglutaminases include Acteva (trade name, manufactured by Ajinomoto Co., Inc.). The transglutaminase activity used in the present invention can be measured by reacting benzyloxycarbonyl L-glutaminylglycine with hydroxyamine and determining the amount of hydroxamic acid produced. By this measurement 1 × per minute
The transglutaminase activity producing 10 ^-6 mol of hydrixamic acid is defined as one unit. Although the transglutaminase used in the present invention varies depending on the gelatin used, it is preferable to control the molecular weight distribution by adding an amount that produces 1 × 10 ⁻⁶ mol or more of hydroxamic acid to 1 g of gelatin.

As a method of crosslinking gelatin with a crosslinking agent, any crosslinking agent which has hitherto been known as a hardening agent for gelatin can be used. The typical compounds are shown below.

A. Inorganic crosslinking agent (inorganic hardener) Cationic chromium complex; ligands of the complex include hydroxyl group, oxalic acid group, citric acid group, malonic acid group, lactate, tartrate, succinate, acetate, Formate, sulfate,
Chloride, nitrate.

Aluminum salts; especially sulfates, potassium alum, ammonium alum. The above compounds crosslink the carboxyl groups of the gelatin.

B. Organic crosslinking agent (organic hardener) Aldehyde-based crosslinkers; the most commonly used is formaldehyde. Effective cross-linking can also be achieved with dialdehyde, for example, glyoxal and succinaldehyde, particularly glutaraldehyde. Diglycolaldehyde, various aromatic dialdehydes, dialdehyde starch, and dialdehyde derivatives of vegetable gums are also used in the crosslinking of the present invention.

2. N-methylol compounds and other protected aldehyde crosslinkers; N-methylol compounds obtained by condensation of formaldehyde with various aliphatic linear or cyclic amides, ureas and nitrogen-containing heterocycles. Specific examples include 2,3-dihydroxodioxane, acetate of dialdehyde and its hemiacetal, and 2,5-methoxytetrahydrofuran.

3. Ketone crosslinking agents; compounds of diketones and quinones. Well-known diketones include 2,3-butanedione, CH ₃ COCOCH _{3 and the} like. As quinone, p-benzoquinone is well known.

4. Sulfonate and sulfonyl halide; bis (sulfonyl chloride) as a typical compound
And bis (sulfonyl fluoride) s.

5. Active halogen compound; a compound having two or more active halogen atoms. Representative compounds include simple bis-α-chloro or bis-α-bromo derivatives of ketones, esters, and amides, bis (2-chloroethylurea), bis (2-chloroethyl) sulfone, and phosphoramidic halides. .

6. Epoxide; butadioxide is a typical compound.

7. Activated olefins; Many compounds having two or more double bonds, especially unsubstituted vinyl groups activated by adjacent electron-withdrawing groups, are effective as gelatin crosslinkers. Examples of this compound include divinyl ketone, resorcinol bis (vinyl sulfonate), 4,
6-bis (vinylsulfonate), 4,6-bis (vinylsulfonyl) -m-xylene, bis (vinylsulfonylalkyl) ether or amine, 1,3,5-triacryloylhexahydro-s-triazine, diacrylamide , 1,3-bis (acryloyl) urea and the like.

8. s-Triazine compound; a compound represented by the following general formula (HI).

[0047]

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In the formula, R ¹ is a hydroxyl group, an —OM group (M is a monovalent metal atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, 2-ethylhexyl), and —N (R ² ) ( R ³ )
Groups (R ² and R ³ each represent an alkyl group having 1 to 10 carbon atoms;
Represents an aryl group having 6 to 15 carbon atoms, which may be the same or different. ), -NHCOR ⁴ (R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and 6 carbon atoms.
-20 represents an arylthio group. ) Or 1 carbon
Represents up to 20 alkoxy groups. In addition, the general formula (H-
The cyanuric chloride hardeners represented by I) are described in JP-B-47-6151, JP-B-47-33380 and JP-B-47-33380.
-25411 and JP-A-56-130740. JP-B-53-2726 and JP-A-50-61 having a structure similar to that of the compound of the formula (HI)
Compounds described in JP-A-219-56 and JP-A-56-27135 are also useful in the present invention.

9. Vinyl sulfone compounds; compounds represented by the following general formula (H-II).

[0050]

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In the above general formula, X ¹ and X ² represent —CH ＝ C
H ₂ or —CH ₂ CH ₂ Y, and X ¹ and X ² may be the same or different. Y represents a group substituted with a nucleophilic group or capable of leaving in the form of HY by a base (for example, a halogen atom, sulfonyloxy, sulfate monoester, etc.). L is a divalent linking group, which may be substituted. The vinyl sulfone hardener represented by the general formula (H-II) is described in, for example, Japanese Patent Publication No. 47-2.
Nos. 4259 and 50-35807, and JP-A-49-24.
No. 435, No. 53-41221, No. 59-18944
There are detailed descriptions in publications such as

10. Carbamoyl ammonium salt; a compound represented by the following formula (H-III):

[0053]

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Where R¹, R^TwoIs alk having 1 to 10 carbon atoms
(E.g., methyl, ethyl, 2-ethylhexyl
Group), an aryl group having 6 to 15 carbon atoms (for example, phenyl
Group, naphthyl group, etc.), or ara having 7 to 15 carbon atoms.
Alkyl group (for example, benzyl group, phenethyl group, etc.)
I may be the same or different. Also
R ¹, R^TwoCombine with each other to form a heterocycle with the nitrogen atom
It is also preferable to do so. X^-Represents an anion. General formula
Carbamoyl ammonium salt represented by (H-III)
Detailed description of the hardener is described in JP-B-56-128.
Nos. 53 and 58-32699, and JP-A-49-5194.
No. 5, No. 51-59625, No. 61-9641
New

11. Compounds represented by the following formula (H-IV)

[0056]

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[0057] R ^1, R ^2, R ³ and X ^- definition is exactly the same as defined in the general formula (H-III), the compounds detailed in Belgian Patent No. 825,726.

12. Amidinium salt compounds; compounds represented by the following general formula (HV)

[0059]

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R ¹ , R ² , R ³ and R ^{4 each} have 1 to 20 carbon atoms.
, An aralkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may be the same or different. Y represents a group which can be eliminated when the compound represented by the general formula (HV) reacts with a nucleophile, and preferred examples include a halogen atom, a sulfonyloxy group and a 1-pyridinium group. X ^- represents an anion. Amidinium salt hardeners represented by the general formula (H-V) are disclosed in JP-A-60-225148.
The issue has a detailed description.

13. Carbodiimide compounds: compounds represented by the following general formula (H-VI)

[0062]

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In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms (eg, a methyl group or an ethyl group), a cycloalkyl group having 5 to 8 carbon atoms, an alkoxyalkyl group having 3 to 10 carbon atoms, or Represents 7 to 15 aralkyl groups. R
² represents a group defined for R ¹ . These carbodiimide hardeners are described in JP-A-51-126125,
No. 52-48311.

14. Lidinium base compounds; compounds represented by the following formula (H-VII)

[0065]

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In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a group having 7 to 1 carbon atoms.
5 represents an aralkyl group. These groups may be substituted. R ² and R ³ each represent a substituent such as a hydrogen atom, a halogen atom, an acylamide group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, and an aralkyl group; May also be different. It is also preferred that R ² and R ³ combine to form a condensed ring together with the pyridinium ring skeleton. Y represents a group which can be eliminated when the compound represented by the general formula (H-VII) is reacted with a nucleophile. X ^- represents an anion. These pyridinium base hardeners are described in detail in JP-B-58-50699, JP-A-57-44140 and JP-A-57-46538.

15. Pyridinium salt compounds; compounds represented by the following formula (H-VIII)

[0068]

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In the formula, R ¹ and R ² are defined by the general formula (H-II
It is exactly the same as the definition of R ¹ and R ² in I), and R ³ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 15 carbon atoms. X ^-
Represents an anion. Pyridinium salt hardeners represented by the general formula (H-VIII) are described in JP-A-52-544.
No. 27 describes this in detail.

As the hardening agent used in the present invention, in addition to the compounds represented by the above formulas (HI) to (H-VIII), JP-A-50-38540 and JP-A-5-238540 can be used. 9
No. 3470, No. 56-43353, No. 58-1139
No. 29 and U.S. Pat. No. 3,321,313 are also preferable.

Specific examples of the compounds used in the present invention are listed below, but the present invention is not limited to these.

[0072]

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[0073]

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In the production of the gelatin used in the emulsion of the present invention, the crosslinking agent mentioned above is added to the gelatin solution to cause gelatin intermolecular crosslinking. The conditions at that time differ depending on each crosslinking agent, but the reaction conditions can be determined by setting a constant reaction temperature and reaction time and measuring the molecular weight distribution of gelatin by the GPC method. At this time, the progress of crosslinking can be monitored by measuring the viscosity of the gelatin solution. It is desirable that all of the added cross-linking agent is reacted, but if it remains unreacted, the remaining cross-linking agent can be removed by ultrafiltration of the gelatin solution after the cross-linking reaction. The molecular weight distribution of the gelatin of the present invention can be controlled by adjusting the amount of the crosslinking agent added and the conditions of the crosslinking reaction such as the temperature, time and pH of the crosslinking reaction.

As the gelatin of the present invention, gelatin crosslinked by one or a combination of two or more of the above crosslinking agents can be preferably used. The general formula (H-
An s-triazine compound represented by the general formula (HI)
A vinyl sulfone compound represented by the general formula (HI)
Gelatin crosslinked using a carbamoyl ammonium salt represented by II) or a carbodiimide compound represented by formula (H-VI) is preferred. In particular, a vinyl sulfone-based compound represented by the general formula (H-II) is preferable since it has little effect on photographic performance.

As the original gelatin used in the production of the gelatin of the present invention, any of alkali-processed gelatin and acid-processed gelatin can be used, but alkali-processed gelatin is more preferable because it has a low impurity content which adversely affects photographic performance. In particular, it is preferable to use alkali-treated gelatin that has been subjected to deionization treatment or ultrafiltration treatment for removing impurity ions and impurities. Alkali-treated gelatin is also preferred as the original gelatin of the crosslinked gelatin preferably used in the present invention.

US Pat. No. 5,318,889 discloses gelatin having a high molecular weight obtained by crosslinking acid-treated gelatin with a vinyl sulfone compound. The gelatin disclosed in the patent did not reach the molecular weight distribution of the gelatin of the present invention, but in the case of acid-treated gelatin, even when the high molecular weight component was increased to the same level as the gelatin of the present invention, It has been found that there are drawbacks in photographic performance such as a reduction in photographic sensitivity.

The gelatin of the present invention may have been subjected to the following various modification treatments. For example, amino-modified phthalated gelatin, succinated gelatin, trimellit gelatin, pyromellitic gelatin, carboxyl-modified esterified gelatin, amidated gelatin, imidazole-modified formylated gelatin, and methionine group are reduced. Oxidized gelatin and increased reduced gelatin.

The silver halide grains in the photosensitive silver halide emulsion containing the gelatin of the present invention and other emulsions used in the present invention have regular crystals such as cubic, octahedral and tetradecahedral. It may have an irregular crystal form such as a sphere or a plate, have a crystal defect such as a twin plane, or a composite form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 20 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion used in the present invention is, for example, Research Disclosure No. 176
43 (December 1978), pp. 22-23, "1. Emulsion preparation and types" 18716 (November 1979), p. 648, ibid. 307105 (November 1989), 863-8
P. 65, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et Physique)
photograohique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffi
n, Photographic Emulsion Chemistry, Focal Press, 1
966), "Manufacture and coating of photographic emulsions" by Zerikman, published by Focal Press (VLZelikman et al., Making and
Coating Photographic Emulsion, Focal Press, 1964)
It can be prepared using the method described in, for example.

As the silver halide photographic emulsion used in the present invention, US Pat. No. 3,574,628 and US Pat.
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred.

The silver halide grains are prepared using the gelatin of the present invention and / or various gelatins as protective colloids. For gelatin, alkali treatment is usually often used. In particular, it is preferable to use alkali-treated gelatin that has been subjected to deionization treatment or ultrafiltration treatment in which impurity ions and impurities have been removed. In addition to alkali-treated gelatin, acid-treated gelatin, derivative gelatin such as phthalated gelatin and esterified gelatin, and low-molecular-weight gelatin (molecular weight of 1000 to 8)
This includes gelatin decomposed by enzymes, gelatin hydrolyzed by acids and / or alkalis, gelatin decomposed by heat, high molecular weight gelatin (molecular weight of 110,000 to 30
10,000), gelatin having a methionine content of 50 μmol / g or less, gelatin having a tyrosine content of 20 μmol / g or less, oxidized gelatin, and gelatin in which methionine is inactivated by alkylation can be used. A mixture of two or more gelatins may be used. The amount of gelatin used in the grain formation step is generally 1 to 60 g / silver mole, preferably 3 to 40 g / silver mole. Steps after the grain formation step, for example, the concentration of gelatin in the chemical sensitization step,
It is preferably from 1 to 100 g / silver mole, and
g / silver mole is even more preferred.

When the gelatin of the present invention is added as a protective colloid, it may be added at any point during the grain formation as in other gelatins, but is preferably added after nucleation. The addition amount is at least 10% by weight, preferably at least 30%, more preferably at least 50%, based on the total dispersion medium during the formation of the particles. Further, the gelatin of the present invention exhibits a remarkable effect even when added as a dispersed gelatin which is added after washing and desalting of the emulsion. The amount added is 10% by weight or more, preferably 30% or more, more preferably 50% or more, and particularly preferably 100%, of the dispersed gelatin added after washing and desalting. It is effective to add the gelatin of the present invention before coating, but it is particularly effective to add the gelatin before the start of chemical sensitization in the emulsion production step in terms of improvement of aggregation. The addition amount of the gelatin of the present invention is 10% by weight or more, preferably 30% by weight, based on the total dispersant in the emulsion.
% Or more, more preferably 50% or more.

The halogen composition of the grains is arbitrary. For example, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide and mixtures thereof can be used. When the emulsion of the present invention is used in a red-sensitive layer or a green-sensitive layer, the iodine on the surface of the grains is preferably 4 mol% in order to rapidly move dye holes into the inside of the grains.
It is desirable that the content be at least 20 mol%. The iodine content on the particle surface can be measured using ESCA.

In the present invention, tabular grains having an aspect ratio of about 2 or more can be preferably used. The following are tabular silver halide grains (hereinafter referred to as "tabular grains").
Will be described in detail.

The aspect ratio is defined as a value obtained by dividing the equivalent circle diameter of two opposing parallel main planes (diameter of a circle having the same projected area as the main planes) by the distance between the main planes (that is, the thickness of particles). The average value of the number average defined and calculated from the aspect ratio of each particle is used.

The aspect ratio of the tabular grains of the present invention is preferably from 3 to 100. It is more preferably 5 or more and 60 or less, and particularly preferably 8 or more and 30 or less. When the gelatin of the present invention is used, the effect is remarkable with large aspect ratio particles having an aspect ratio of 8 or more, which is preferable.

The proportion occupied by tabular grains having an aspect ratio in the above range is preferably at least 60% of the total projected area. It is more preferably 80% or more, and 90% or more.
% Is particularly preferable.

The diameter (corresponding to a circle) of the tabular grains can be arbitrarily selected, but is preferably from 0.30 to 20 μm, more preferably from 0.5 to 15 μm. When the gelatin of the present invention is used, the effect is remarkable with large-sized particles of 2 μm or more, which is preferable.

The particle thickness is preferably 0.5 μm or less,
It is more preferably 0.4 μm or less, and still more preferably 0.1 μm.
It is not less than 06 μm and not more than 0.3 μm.

The measurement of the particle diameter and the particle thickness can be obtained from an electron micrograph of the particles as described in US Pat. No. 4,434,226.

Tabular grains have an average circle equivalent diameter value divided by the average thickness squared value (value defined as ECD / t ^{2 in} JP-A-3-135335; tabularization ratio) of 5 or more. And more preferably 10 or more, further preferably 25 or more and 250 or less.

In the present invention, the tabular grains preferably have a relative standard deviation of grain size distribution of 35% or less. Here, the relative standard deviation is a variation (standard deviation) of a circle equivalent diameter calculated from a projected area of the tabular grain.
Divided by the average value of equivalent circle diameters calculated from the projected area of the tabular grains, and multiplied by 100. The grain size distribution of the silver halide emulsion composed of a group of grains having a uniform grain morphology and small variation in grain size shows almost a normal distribution, and the standard deviation can be easily obtained. The relative standard deviation of the grain size distribution of the tabular grains is more preferably 30% or less, and even more preferably 25% or less.

The tabular grains whose major surfaces are (100) and (111) are known, and the technique of the present invention can be applied to both. As for the former, U.S. Pat. No. 4,063,951 and JP-A-5-28164 relate to silver bromide.
No. 0, and with respect to silver chloride, EP 534,
395A1 and U.S. Pat. No. 5,264,337. The latter tabular grains are grains having various shapes having one or more twin planes described above. Regarding silver chloride, U.S. Pat. Nos. 4,399,215 and 4,9
Nos. 83,508 and 5,183,732;
137632 and 3-116113.

The tabular grains can be prepared by a known method. The preparation of monodisperse tabular grains is described in JP-A-63-11928. Monodisperse hexagonal tabular grains are disclosed in
No. 151618. Circular monodisperse tabular grain emulsions are described in JP-A-1-131541. Japanese Patent Application Laid-Open No. 2-838 discloses that the total projected area is 95%.
% Or more are occupied by tabular grains having two twin planes parallel to the main plane, and the size distribution of the tabular grains is monodispersed. European Patent 514,
742A1 discloses a tabular grain emulsion prepared using a polyalkylene oxide block copolymer and having a grain size variation coefficient of 10% or less.

The silver halide grains used in the present invention are:
Dislocation lines may be present in the grains. A technique for controlling the introduction of dislocations into silver halide grains is described in JP-A-63-220238. According to the description of this publication, a specific high iodine phase is provided inside tabular silver halide grains having an average grain diameter / grain thickness ratio of 2 or more, and the outside has a lower iodine content than the high iodine phase. Dislocations can be introduced by covering with a phase. By introducing the dislocation, effects such as an increase in sensitivity, an improvement in storage stability, an improvement in stability of a latent image, and a reduction in pressure fog can be obtained. According to the invention described in this publication, dislocations are mainly introduced at the edges of tabular grains. The tabular grains having dislocations introduced at the center are described in US Pat. No. 5,238,796. Further, JP-A-4-348337 discloses normal crystal grains having dislocations therein. The publication discloses that epitaxy of silver chloride or silver chlorobromide is formed in normal crystal grains, and that the epitaxy can be introduced by physical ripening and / or conversion by halogen. The introduction of such dislocations has the effects of increasing sensitivity and reducing pressure fog.

The dislocation lines in the silver halide grains are, for example,
JF Hamilton, Photo.Sci. Eng., 11, 57 (1967)
And T. Shiozawa, J. Soc. Photo. Sci. Japan, 35, 21
3 (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope, and the sample is placed so as to prevent damage (printout) by electron beams. Observation is performed by a transmission method in a cooled state. At this time, the thicker the particle, the more difficult it is for an electron beam to pass. Therefore, it is more clear to use a high-pressure electron microscope (200 kv or more for a particle having a thickness of 0.25 μm) to observe more clearly. it can. From the photograph of the particles obtained by such a method, the position and number of dislocation lines for each particle when viewed from a plane perpendicular to the main plane can be obtained.

In the present invention, it is preferable that 50% or more of the total projected area of the silver halide grains has 10 or more dislocation lines per grain. In particular, in the case of tabular grains having an aspect ratio of about 2 or more, the dislocation lines are located almost uniformly over the entire area on the outer periphery of the tabular grains, even if the dislocation lines are located almost uniformly on the outer periphery. You may have. That is, in the case of hexagonal tabular grains, for example, it may be limited to only the vicinity of six vertices,
The dislocation lines may be limited only to the vicinity of the vertices. Conversely, dislocation lines may be limited to only sides excluding the vicinity of the six vertices. Further, dislocation lines may be formed on the main plane of the tabular grains.

The emulsions used in the present invention can use any of the usual dopants known to be useful for silver halide face-centered cubic crystal lattice structures. Common dopants include Fe, Co, Ni, Ru, Rh, P
d, Re, Os, Ir, Pt, Au, Hg, Pb, Tl
and so on. These dopants are the host emulsion and / or
Alternatively, it can be present in a silver salt epitaxially arranged on the grain surface.

Next, the hole trap zone preferably used in the emulsion of the present invention will be described. The hole trap zone in the present invention refers to a region having a function of capturing a so-called hole, for example, a hole (hole) generated as a pair with a photoelectron generated by photoexcitation. There are various methods for providing such a hole trap zone. In the present invention, it is desirable to provide the hole trap zone by reduction sensitization.

In the present invention, the inside of the particle is a region inside 90% of the volume of one particle. The particle surface is a region outside the inside of the particle. In the present invention, the hole trap zone may be located only inside the particle, inside the particle, on the particle surface, or only on the particle surface. However, since the reduced silver nuclei are easily destroyed by oxygen and moisture in the air, the hole trap zone is more preferably inside the grains when the emulsion itself or the photosensitive material is stored for a long period of time.

The process for producing a silver halide emulsion is roughly classified into processes such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. The reduction sensitization can be applied to the silver halide emulsion in basically any step of each production step. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, during growth, or may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains. Here, growing is also referred to as a method of performing reduction sensitization in a state where silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. The method also includes a method of further growing after subjecting to reduction sensitization in a heated state.

In the present invention, reduction sensitization refers to a method of adding a known reducing agent to a silver halide emulsion, a method of growing or ripening in a pAg1 to 7 low pAg atmosphere called silver ripening, or a high pH ripening. PH 8-1 called
Either the method of growing in a high pH atmosphere or the method of ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

As the reduction sensitizer, there are known a silver salt, an amine and a polyamic acid, a hydrazine derivative, a formamidine sulfinic acid, a silane compound, a borane compound, an ascorbic acid and a derivative thereof. In the present invention, these known compounds can be selected and used.
More than one compound may be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. The amount of the reduction sensitizer to be added depends on the type of the reduction sensitizer and the emulsion production conditions, so it is necessary to select the amount of the reduction sensitizer, but the range of 10 ^-7 to 10 ^-3 mol per mol of silver halide is appropriate. . However, in the case of an ascorbic acid compound, 5 × 10
The range of ^-5 to 1 × 10 ^-1 mol is appropriate.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferable method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

In order to arrange the hole trap zone only inside the particle, it is effective to contain at least one compound selected from the compounds represented by the following general formulas (A), (B) and (C).

General formula (A) R—SO ₂ S—M General formula (B) R—SO ₂ S—R ¹ General formula (C) R—SO ₂ S L _m —SSO ₂ —R ² R, R ¹ and R ² may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group; M represents a cation; L represents a divalent linking group; Or 1. The compounds of the general formulas (A) to (C) are
It may be a polymer containing a divalent group derived from the structure shown in (C) as a repeating unit. In the general formula (B), R and R ¹ may be bonded to each other to form a ring, and in the general formula (C), R, R ² and L may be bonded to each other to form a ring.

Compounds of general formulas (A), (B) and (C)
To describe the object in more detail, R, R ¹And R^TwoIs aliphatic
In the case of groups, saturated or unsaturated, straight-chain, branched or cyclic
An aliphatic hydrocarbon group, preferably having 1 carbon atom
22 alkyl groups, alkenyl having 2 to 22 carbon atoms
Alkynyl group having 2 to 22 carbon atoms,
May have a substituent. As the alkyl group,
For example, methyl, ethyl, propyl, butyl, pentyl,
Hexyl, octyl, 2-ethylhexyl, decyl, de
Decyl, hexadecyl, octadecyl, cyclohexyl
Isopropyl, t-butyl. Alkene
The aryl group includes, for example, allyl and butenyl.
Examples of the alkynyl group include propargyl and butynyl.
can give.

The aromatic groups represented by R, R ¹ and R ² include monocyclic or condensed ring aromatic groups, preferably those having 6 to 20 carbon atoms, such as phenyl and naphthyl. Can be These may be substituted.

As the heterocyclic group for R, R ¹ and R ² ,
A 3- to 15-membered ring having at least one hetero element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, for example, a pyrrolidine ring, a piperidine ring, a pyridine ring,
Tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, tellurazole ring, triazole ring, benzotriazole ring, tetrazole ring, oxazi An azole ring and a thiadiazole ring are exemplified.

Examples of the substituent for R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy), and an aryl group (eg, phenyl, Naphthyl, tolyl), hydroxy group, halogen atom (eg, fluorine, chlorine, bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (Eg, acetyl, propionyl, butyryl, valeryl), a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), an acylamino group (eg, acetylamino, benzamino), a sulfonylamino acid (eg, methanesulfonylamino, benzenesulfonylamino), Examples include an acyloxy group (eg, acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group, and the like.

The divalent linking group represented by L includes
An atom or an atomic group containing at least one selected from C, N, S and O. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-,
-S -, - NH -, - CO -, - SO 2 - is made of a single or a combination thereof.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group for L include-(CH ₂ ) _n- (n = 1 to 12) and -CH ₂ -C
H = CH—CH ₂ —, —CH ₂ C≡CCH ₂ —, and a xylylene group. As the divalent aromatic group for L,
For example, phenylene and aphthylene are mentioned.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), a phosphonium ion (tetraphenylphosphonium), and a guanidine group.

Specific examples of the compound represented by formula (A), (B) or (C) are shown below, but it should not be construed that the invention is limited thereto.

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

The above specific compounds are described in JP-A-54-10
No. 19 and British Patent No. 972,211.

The compounds represented by formulas (A) to (C) are preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. 10 ^-6 to 10 ^-2 , especially 1
An addition amount of 0 ^-5 to 10 ^-3 mol is preferred.

The compounds represented by the general formulas (A) to (C) can be added during the production process by a method usually used when adding an additive to a photographic emulsion. For example, a water-soluble compound is an aqueous solution having a suitable concentration, and a compound that is water-soluble or hardly soluble in water is a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, and amides. Among them, it can be dissolved in a solvent that does not adversely affect the photographic properties and added as a solution.

The compounds represented by formulas (A) to (C) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization. Preferred is a method in which a compound is added before or during reduction sensitization. Particularly preferred is a method of adding during the grain growth.

Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during the formation of particles. The compounds of the general formulas (A) to (C) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions.
It is also a preferable method to add the compounds of the general formulas (A) to (C) in several portions with the formation of particles, or to add them continuously for a long time.

Among the compounds represented by formulas (A) to (C), the most preferred compound for the present invention is a compound represented by formula (A).

The hole trap zone is arranged only inside the particles.
Another method of placing is to use an oxidizing agent.
The oxidizing agent may be inorganic or organic. Nothing
Oxidants for the machine include ozone, hydrogen peroxide, and
Additives (eg, NaBO_Three・ H_TwoO_Two・ 3H_TwoO, 2Na
CO_Three・ 3H_TwoO_Two, Na_FourP_TwoO₇・ 2H_TwoO_Two, 2Na _TwoS
O_Four・ H_TwoO_Two・ H_TwoO), peroxyacid salts (eg, K_Two
S_FourO₈, K_TwoC_TwoO₆, K_FourP_TwoO₈) 、 Peroxy complex compound
Object (eg, K_Two[TiO_TwoC_TwoO_Four] 3H_TwoO, 4K_TwoSO
_Four・ TiO_Two・ OH ・ 2H_TwoO, Na_Three[VOO_Two(C
_TwoO_Four) 2.6H_TwoO]), permanganate (eg, K
MnO_Four), Chromates (eg, K_TwoCr_TwoO₇) And other acids
Phosphates, halogen elements such as iodine and bromine, perhalates
(Eg, potassium periodate), high valent metal salts
(For example, potassium hexacyanoferrate).
As the organic oxidizing agent, quinone such as p-quinone is used.
, Organic peroxides such as peracetic acid and perbenzoic acid, active halogen
Compounds that release anion (eg, N-bromosuccinimide)
, Chloramine T, chloramine B).

Preferred oxidizing agents in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonic acids and quinones, and particularly preferably thiols represented by the above formulas (A) to (C). Sulfonic acid compounds are most preferred, and compounds represented by formula (A) are most preferred.

In order to arrange the hole trap zone on the particle surface, the reduction sensitization may be performed after 90% or more of the host particles are formed.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. No. 17643, ibid. No. 18716 and the same No. 307105, etc., and the relevant locations are summarized in the table below.

The light-sensitive silver halide emulsion of the present invention contains B /
The invention can be applied to various color photosensitive materials such as W photosensitive materials, general or movie color negative films, slide or television color reversal films, color papers, color positive films, and color reversal papers.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic such as grain shape and sensitivity can be used in a mixture in the same layer. Further, the emulsion of the present invention and the emulsion of the present invention can be mixed and used in the same layer.

In the present invention, silver halide grains previously fogged can be used. U.S. Pat. No. 4,082,
No. 553, U.S. Pat. No. 4,626,498, and JP-A-59-2.
No. 14,852, the fogged silver halide grains and colloidal silver can be preferably used in a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or surface of the grains fogged is described in US Pat.
No. 6,498, and JP-A-59-214852.

The silver halide forming the internal nucleus of the core / shell type silver halide grains having the inside of the grains fogged may have the same halogen composition or different halogen compositions. Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.75 μm.
m, particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited, but may be regular grains or polydispersed emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is ± 10% of the average grain size). (Having a particle diameter of 40% or less).

In the present invention, non-light-sensitive fine silver halide grains can be used. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the development process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or
Alternatively, it may contain silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide. Average grain size of fine grain silver halide (Average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, and 0.02 to 0.5 μm.
2 μm is more preferred.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the fine grain silver halide grain-containing layer.

The amount of silver applied to the light-sensitive material of the present invention was 10 g /
m ² or less, more preferably 6 g / m ² or less.

The light-sensitive silver halide emulsion of the present invention is provided with at least one blue-sensitive layer, green-sensitive layer and red-sensitive layer on a support. It is particularly preferably applied to certain color light-sensitive materials. It is also suitable for a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784.

The light-sensitive material of the present invention is not particularly limited in the number and order of the silver halide emulsion layer and the non-light-sensitive 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. Wherein the light-sensitive layer is a unit light-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,
In general, the arrangement of the unit photosensitive layers is provided in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer in order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layers are described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, and JP-A-61-113440.
It may contain a coupler or a DIR compound as described in 1-20037 and 61-20038, and may contain a color mixture inhibitor as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. JP-A-57-112751, JP-A-62-20035
As described in JP-A Nos. 0 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity 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-55-34932, 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 No. 6, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest 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 such three layers having different sensitivities, as described in JP-A-59-202264, the medium-sensitive emulsion layer / high The layers may be arranged in the order of a light-sensitive emulsion layer / a light-sensitive emulsion layer. In addition, high-speed emulsion layer / low-speed emulsion layer /
Medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer /
They may be arranged in the order of a high-sensitivity emulsion layer and the like. Also,
In the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is 30 ° C. in a color developing solution,
90% of the maximum swollen film thickness reached when treated for 3 minutes 15 seconds
Is defined as the time required for the film thickness itself to reach １ ／, where is the saturated film thickness. The film thickness is 25 ° C. and relative humidity 55.
% Adjustment means a film thickness was measured with a humidity (2 days), T _1/2 is,
Photographics by A. Green and others
Science and Engineering (Photogr. Sc
i. Eng.), Vol. 19, 2, 124-129, can be used for the measurement. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 15
0-400% is preferred. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer having a total dry film thickness of 2 to 20 μm (referred to as a back layer) is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of this back layer is 150 to
500% is preferred. It is also preferable to provide the following magnetic recording layer.

The transparent magnetic recording layer preferably used in the light-sensitive material of the present invention will be described. The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support.

[0152] magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite, C
O-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _3, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. 20 for non-surface area by S _BET
m is preferably not less than ² / g, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0
× 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-160332. JP-A-4-259911 and 5-816
No. 52, magnetic particles having a surface coated with an inorganic or organic substance can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferred. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3 mol of tolylene diisocyanate)
Reaction product of 1 mol of trimethylolpropane and trimethylolpropane) and polyisocyanates formed by condensation of these isocyanates.
No. 357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin-type mill, an annular-type mill, etc. are preferably used, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm
３3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.1 to 3 g / m ² .
01 to ² g / m ² , more preferably 0.02 to 0.5
g / m ² . The transmission yellow density of the magnetic recording layer is
0.01 to 0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, anti-adhesion, and head polishing, or may provide another functional layer to impart these functions, and at least one of the particles has a Mohs hardness of 5 or more. The abrasive of non-spherical inorganic particles is preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For a light-sensitive material having a magnetic recording layer, see US Pat. No. 5,336,589,
Nos. 5,250,404 and 5,229,259
No. 5,215,874, European Patent No. 466,1
No. 30.

The photosensitive material having the above-described magnetic recording layer has a drawback that storage stability with time (sensitivity increase, increase in fog) is deteriorated, but the storage stability with time is improved by the present invention described above.

The photographic additives that can be used in the present invention are described in Research Disclosure (RD), and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column Brightener page 24 page 647 right column page 868 5. 5. Light absorber, pages 25 to 26, page 649, right column, page 873, filter dye, 頁 650, left column, ultraviolet absorber 6. Binder page 26 page 651 left column pages 873 to 874 7. Plasticizer, lubricant page 27 page 650 right column page 876 8. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 right column 876-877 Inhibitors Matting agents pages 878-879.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferred.

Yellow coupler: EP 502,4
Couplers represented by formulas (I) and (II) of No. 24A; Couplers represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); EP 568 U.S. Pat. No. 5,066,576, a coupler represented by general formula (I) at column 45, line 45-55; a coupler represented by formula (I) of claim 1, U.S. Pat. No. 5,066,576; Couplers of the general formula (I) of paragraph 0008; EP 498,38
Couplers described in claim 1 on page 40 of 1A1 (especially D-35 on page 18); couplers of the formula (Y) on page 4 of EP 447,969 A1 (especially Y-1).
(P. 17), Y-54 (p. 41)); U.S. Pat.
Nos. 76, 219, column 7, lines 36 to 58, formula (II) to
Couplers represented by (IV) (particularly II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler: JP-A-3-39737
No. (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,2
No. 57 [A-4] -63 (p. 134), [A-4]-
73, 75 (p. 139); M-4, 6 (p. 26) and M-7 (p. 27) of EP 486,965; M-45 (p. 19) of EP 571,959A; JP 5
-204106 (M-1) (p. 6);
No. 62631, paragraph 0237, M-22.

Cyan coupler: JP-A-4-208443
No. CX-1,3,4,5,11,12,14,15
(Pages 14 to 16); C-7 in JP-A-4-43345;
10 (p. 35), 34, 35 (p. 37), (I-1),
(I-17) (pp. 42-43); JP-A-6-67385
2. A coupler represented by the general formula (Ia) or (Ib) according to claim 1.

Polymer coupler: JP-A-2-44345
Nos. P-1, P-5 (p. 11).

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,873B.
And those described in West German Patent No. 3,234,533 are preferred.

Couplers for correcting unnecessary absorption of color dyes are described in Yellow Colored Formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257 A1. Cyan coupler (especially Y on page 84)
C-86), yellow colored magenta coupler ExM-7 (p. 202) and EX-1 (24
9), EX-7 (page 251), U.S. Pat.
Magenta colored cyan couplers CC-9 (column 8) and CC-13 (column 10) described in 3,069, U.S. Pat. No. 4,837,136 (2) (column 8),
Formula (A) of claim 1 of WO 92/11575
A colorless masking coupler (especially 36 to 4)
Exemplary compounds on page 5) are preferred.

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following.

Development inhibitor releasing compound: EP 37
Formula (I), (II), and
Compounds represented by (III) and (IV) (particularly T-101
(Page 30), T-104 (page 31), T-113 (36
Page), T-131 (page 45), T-144 (page 51),
T-158 (p. 58)), EP 436,938A.
No. 2, page 7 (especially D-49 (p. 51)) and compounds represented by formula (I) in EP 568,037A (especially (23) (11)
P.)), Compounds represented by formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195 A2 (especially I- (1) on page 29).

Bleaching accelerator releasing compounds: EP 31
Compounds represented by formulas (I) and (I ') on page 5, No. 0,125A2 (especially (60) and (61) on page 61) and formula (I) of claim 1 of JP-A-6-59411. (Especially (7) (p. 7)).

Ligand releasing compound: US Pat. No. 4,55
A compound represented by LIG-X described in claim 1 of No. 5,478 (especially, a compound in column 12, lines 21 to 41).

Leuco dye releasing compounds: US Pat. No. 4,7
Compounds 1 to 6 in columns 3 to 8 of No. 49,641.

Fluorescent dye releasing compound: US Patent No. 4,77
No. 4,181, the compound represented by COUP-DYE of claim 1 (especially compounds 1 to 11 in columns 7 to 10).

Development accelerator or fogging agent releasing compound: Formula (1) in column 3 of US Pat. No. 4,656,123;
Compounds represented by (2) and (3) (especially (I-22) in column 25) and ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2.

Compounds which release a group which becomes a dye only after leaving: compounds represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y-1 to Y- of columns 25 to 36) 19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: JP-A-62-215272
No. P-3, 5, 16, 19, 25, 30, 42, 4
9, 54, 55, 66, 81, 85, 86, 93 (14
0-144).

Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363.

Oxidized developing agent scavenger: A compound represented by the formula (I) in columns 2 to 54 to 62 of US Pat. No. 4,978,606 (especially I- (1), (2),
(6), (12) (columns 4-5), U.S. Pat.
No. 23,787, column 5 lines 5 to 10 (especially compound 1 (column 3).

Antistaining agent: EP 298321
Formulas (I) to (III) on page 4, lines 30 to 33 of No. A, especially I-
47, 72, III-1, 27 (24-48).

Antifading agent: EP 298,321A
A-6,7,20,21,23,24,25,2
6, 30, 37, 40, 42, 48, 63, 90, 9
2,94,164 (pp. 69-118), U.S. Pat.
Nos. 122, 444, columns 25 to 38, II-1 to III-
23, especially III-10, 8 to 1 of EP471, 347A
I-1 to III-4, especially II-2, page 2, U.S. Pat.
Nos. 39,931 columns 32-40 A-1 to 48, especially A-39,42.

Materials for Reducing the Use of Color Enhancing Agents or Color Mixing Prevention Agents: European Patent No. 41,132A, 5 to 24
Pages I-1 to II-15, especially I-46. Formalin scavenger: EP 477,932
No. A, pages 24 to 29, SCV-1 to 28, especially SCV-
8.

Hardener: 17 of JP-A-1-214845
Pp. H-1,4,6,8,14, U.S. Pat. No. 4,61
No. 8,573, columns 13 to 23, formulas (VII) to (XI)
Compounds (H-1 to 54) represented by I),
Compounds (H-1 to 76) represented by the formula (6) at the lower right of page 8 of 214852, especially H-14, U.S. Pat.
25. The compound according to claim 1 of claim 25,287.

Development inhibitor precursor; JP-A-62-1
No. 68139, p. 24, 37, 39 (pages 6-7); U.S. Pat. No. 5,019,492, claims 1; Preservatives and fungicides: I- of columns 3 to 15 of U.S. Pat. No. 4,923,790.
1 to III-43, especially II-1, 9, 10, 18, III-2
5. Stabilizers, antifoggants: U.S. Pat. No. 4,923,7
No. 93, columns 6 to 16, I-1 to (14), especially I-
1,60, (2), (13), U.S. Pat. No. 4,952,
No. 483, columns 25-32, compounds 1-65, especially 3
6.

Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324.

Dyes: 15 to 15 of JP-A-3-156450
A-1 to b-20 on page 18, especially a-1, 12, 18,
V-1, 1-2 on pages 27, 35, 36, b-5, 27-29
3, especially V-1, 33- of EP 445627A.
F-I-1 to F-II-43 on page 55, especially F-I-11,
II on pages 17 to 28 of F-II-8, EP457, 153A
I-1 to 36, especially III-1,3, International Patent No. 88/04
No. 794, Microcrystal dispersion of Dye-1 to 124 of Dye-1 to 124, Compounds 1 to 22 of EP 319,999A, pp. 6 to 11, especially Compound 1, EP 519,306.
Compound D-1 represented by Formula (1) to (3) of No. A
~ 87 (pages 3-28), U.S. Patent No. 4,268,622.
Nos. 1 to 22 represented by the formula (I) (columns 3 to
10), compounds (1) to (31) represented by the formula (I) in U.S. Pat. No. 4,923,788 (columns 2 to 9).

UV absorber: Compounds (18b) to (18r), 1 represented by formula (1) in JP-A-46-3335.
01-427 (pages 6-9), EP 520938A
(3) to (66) (1)
0-44) and a compound HBT represented by the formula (III)
-1 to 10 (p. 14), compounds (1) to (31) represented by the formula (I) in EP 521823A (columns 2 to 9).

The light-sensitive material of the present invention can be obtained from Research Disclosure No. No. 17643, pages 28 to 29; No. 18716, 651 left column to right column;
The development can be carried out by a usual method described on pages 880 to 881 of 307105.

The processing solution for a color negative film used in the present invention will be described. The color developing solution used in the present invention is described in JP-A-4-121739, page 9, upper right column 1
The compounds described in line 4 to page 11, lower left column, line 4 can be used. Particularly, color developing agents for rapid processing include 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline and 2-methyl-4-aniline.
[N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl-4- [N-ethyl-N-
(4-Hydroxybutyl) amino] aniline is preferred.

These color developing agents are used in an amount of 0.01 to 1 liter of a color developing solution (hereinafter also referred to as “L”).
It is preferably used in the range of 0.08 mol, particularly 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol.
It is preferred to use it in the molar range. It is preferred that the replenisher of the color developing solution contains a color developing agent having a concentration of 1.1 to 3 times this concentration, particularly 1.3 to 2.5 times.
It is preferred that the content be doubled.

As a preservative for the color developing solution, hydroxylamine can be used in a wide range. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. Hydroxylamine derivatives having a group are preferred, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.2 mol.
It is preferably used in an amount of 15 mol, more preferably 0.04 to 0.1 mol. In the replenisher, as in the case of the color developing agent, 1.1 to 3 of the mother liquor (processing tank solution) is used.
It is preferable to contain a preservative at twice the concentration.

In the color developing solution, a sulfite is used as an agent for preventing tartarization of the oxide of the color developing agent. The sulfite is preferably used in a range of 0.01 to 0.05 mol per liter, and particularly preferably in a range of 0.02 to 0.04 mol per liter. In the replenisher, it is preferable to use the replenisher at a concentration of 1.1 to 3 times the concentration.

The pH of the color developing solution is 9.8-11.
The range of 0 is preferable, and especially 10.0 to 10.5 is preferable.
It is preferable to set a high value in the range of 1.0 to 1.0. To maintain such a pH stably, carbonate,
Known buffers such as phosphates, sulfosalicylates, borates and the like are used.

The replenishment amount of the color developing solution is preferably from 80 to 1300 ml per 1 m ² of the light-sensitive material (hereinafter also referred to as “mL”), but is preferably smaller from the viewpoint of reducing environmental pollution load. Specifically, 80-600
mL, more preferably 80 to 400 mL.

The bromide ion concentration in the color developing solution is usually from 0.01 to 0.06 mol per liter. However, while maintaining sensitivity, fog is suppressed to improve discrimination, and the granularity is improved. 1L for the purpose of improving
Is preferably set to 0.015 to 0.03 mol per unit. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions.

C = A−W / V C: Bromide ion concentration in the color developing replenisher (mol / L) A: Target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² exposure Amount (mol) of bromide ion eluted from the light-sensitive material into the color developer when the material is color-developed V: replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material.

When the replenishment rate is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by octanediol.

The processing solution having bleaching ability in the present invention includes, from page 4, lower left column, line 16 to page 4 of JP-A-4-125558.
The compounds and processing conditions described on page 7, lower left column, line 6, can be applied.

The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more.
Nos. 694 and 5-173312 are preferred, and in particular, 1,3-diaminopropanetetraacetic acid,
A ferric complex salt of the compound of Example 1 on page 7 of 17312 is preferred.

Further, in order to improve the biodegradability of the bleaching agent, JP-A-4-251845 and JP-A-4-268552 can be used.
Nos., EP 588,289, and 591,934.
It is preferable to use a compound ferric complex salt described in JP-A-6-208213 as a bleaching agent. The concentration of these bleaching agents is from 0.05 to 1 per liter of a solution having bleaching ability.
It is preferably 0.3 mol, and in particular, it is preferably designed to be 0.1 mol to 0.15 mol for the purpose of reducing the amount discharged to the environment. If the bleaching solution is a bleaching solution,
Preferably, 0.2 to 1 mol of bromide is contained per liter, particularly preferably 0.3 to 0.8 mol.

The replenisher of the solution having the bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant.

C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (treatment tank solution) C _P : During treatment the concentration of consumed components V _1: amount of replenisher having bleaching ability for the light-sensitive material of 1m _² (mL) V ^2: amount carried from previous bath by the photographic material of 1 m ² (m
L).

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, Japanese Unexamined Patent Publication No.
No. 95630, RDNo. 17129, U.S. Pat. No. 3,893,858. It is also preferred to use known bleaching accelerators.

The bleaching solution contains 50 to 50 m ^{2 of} photosensitive material.
Preferably, 1000 mL of the bleaching replenisher is replenished, particularly preferably 80 to 500 mL, more preferably 100 to 300 mL. Further, it is preferable to perform aeration on the bleaching solution.

For the processing solution having a fixing ability, the compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied.

In particular, in order to improve the fixing speed and the preservability, a processing solution having a fixing ability by using the compounds represented by the general formulas (I) and (II) of JP-A-6-301169, alone or in combination. Is preferably contained. It is also preferable to use a sulfinic acid described in JP-A 1-2224762, in addition to p-toluenesulfinic acid salt, from the viewpoint of improving preservation.

It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property. However, from the viewpoint of reducing environmental pollution, ammonium is reduced or reduced to zero. Is more preferred.

In the bleaching, bleach-fixing and fixing steps, it is particularly preferred to perform jet stirring described in JP-A-1-30959.

The replenishment rate of the replenisher in the bleach-fixing or fixing step is from 100 to 1000 mL, preferably from 150 to 700 mL, particularly preferably from 20 to 1 mL per m ² of the light-sensitive material.
0-600 mL.

In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank is cascaded to form a multistage countercurrent system. In general, a two-tank cascade configuration is efficient in view of the balance with the size of the developing machine, and the ratio of the processing time in the former tank to the latter tank is in the range of 0.5: 1 to 1: 0.5. It is particularly preferable that the ratio be in the range of 0.8: 1 to 1: 0.8.

In the bleach-fixing solution and the fixing solution, a free chelating agent not forming a metal complex is preferably present from the viewpoint of the improvement of preservation. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

The washing and stabilizing steps are described in JP-A-4-125558, page 12, lower right column, line 6 to 1
The contents described in page 16, lower right column, line 16, can be preferably applied. Particularly, in place of formaldehyde, azolylmethylamines described in European Patent Nos. 504,609 and 519,190, and JP-A-4-3629 are used in place of formaldehyde.
Use of N-methylolazoles described in No. 43 or dimerization of the magenta coupler to form a surfactant-free liquid containing no image stabilizer such as formaldehyde is preferred from the viewpoint of preserving the working environment. preferable.

Further, in order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, see Japanese Patent Application Laid-Open No. 6-289559.
The stabilizer described in the above item can be preferably used.

The replenishing amount of the washing and the stabilizing solution can be adjusted according to the photosensitive material 1
80 to 1000 mL per m ² is preferable, and
The range is preferably from 500 mL, more preferably from 150 mL to 300 mL, from the viewpoint of both securing the washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment carried out with such a replenishing amount, a known method such as thiabendazole, 1,2-benzisothiazolin-3-one and 5-chloro-2-methylisothiazolin-3-one is used to prevent the growth of bacteria and fungi. It is preferable to use water deionized with an antifungal agent, an antibiotic such as gentamicin, or an ion exchange resin. It is more effective to use deionized water in combination with antibacterial agents and antibiotics.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, JP-A-3-53246, and JP-A-3-53246
No. 55542, No. 3-121448, No. 3-1260
It is also preferable to reduce the replenishment rate by performing the reverse osmosis membrane treatment described in No. 30. In this case, the reverse osmosis membrane is preferably a low-pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of the evaporation of the processing solution disclosed in the Japan Institute of Technology, Technical Publication No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for the evaporation correction is preferably collected from a water replenishing tank, and in that case, it is preferable to use deionized water as the water replenishing water.

[0216] As the treating agent used in the present invention, those described in page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. Further, as a developing machine used for this, a film processor described on page 3, right column, lines 22 to 28 is preferable.

Specific examples of preferred processing agents, automatic developing machines, and evaporation correction methods for carrying out the present invention are described in the above-mentioned published technical report, from page 5, right column, line 11 to page 7, right column, last line. Have been.

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. An example of such a treating agent is disclosed in
No. -17453, JP-A-4-19655 and JP-A-4-230748 describe vacuum-packaged powders or granules, and JP-A-4-2219.
No. 51 discloses granules containing a water-soluble polymer.
1-61837 and JP-A-6-102628 disclose tablets, and JP-T-57-500485 discloses a paste-like treatment agent.
From the viewpoint of simplicity at the time of use, it is preferable to use a liquid that has been prepared in advance at a concentration in a state of use.

[0219] In the containers for storing these treating agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeation. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers with a thickness of 500-1500 μm,
It is preferable that the oxygen permeability be 20 mL / m ² · 24 hrs · atm or less.

Next, the processing solution for the color reversal film used in the present invention will be described. Regarding the processing for a color reversal film, see page 6, line 1 to page 10, line 5 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Corporation
Line and page 15, line 8 to page 24, line 2, all of which can be preferably applied.

In processing a color reversal film, an image stabilizer is contained in a conditioning bath or a final bath. Examples of such an image stabilizer include, in addition to formalin, sodium formaldehyde sodium bisulfite and N-methylolazole. From the viewpoint of a work site, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferable. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

As a preferred color reversal film treating agent containing the above-mentioned contents, Eastman Kodak E-6
Examples of the treating agent include CR-56 treating agent manufactured by Fuji Photo Film Co., Ltd.

Suitable supports that can be used in the present invention are described, for example, in Research Disclosure No. 176
No. 43, page 28, ibid. No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples other than those described above, refer to Published Technical Report, Official Technical Publication No. 94-6023 (Invention Association). 1994.
3.15. )It is described in. The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components.
1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A as a diol;
Bisphenol etc. are mentioned. As this polymer,
Examples include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexane dimethanol terephthalate. Particularly preferred is 2,6-naphthalenedicarboxylic acid in an amount of 50 mol% to 10 mol%.
It is a polyester containing 0 mol%. Among them, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester that can be used in the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg-20 ° C. or more and less than Tg, in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is from 0.1 hour to 1500 hours, more preferably from 0.5 hour to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent.

An ultraviolet absorbent may be incorporated in this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to adhere the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoating method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including a copolymer starting from a simple monomer selected from among maleic anhydride, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm)
m) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acids and carboxylate, polymers including sulfonate,
Examples include cationic polymers and ionic surfactant compounds.

The most preferred antistatic agent is Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₂ , In ₂ O ₃ , SiO
₂ , a particle size of at least one selected from MgO, BaO, MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. 0
01-1.0 μm crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.)
And further, sol-shaped metal oxides or fine particles of these composite oxides. As the content in the photosensitive material,
It is preferably from 5 to 500 mg / m ² , particularly preferably from 10 to 500 mg / m ^2.
３５０350 mg / m ² . The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is from 1/300 to 1
00/1 is preferred, more preferably 1/100 to 10
0/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

The slip agents usable in the present invention include polyorganosiloxanes, higher fatty acid amides, metal salts of higher fatty acids, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane and polydiethylsiloxane. Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio), polystyrene particles, etc. are preferable. The particle size is preferably 0.8 to 10 μm, and the narrower the particle size distribution, the better. Preferably, 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size.
It is also preferable to simultaneously add fine particles of 8 μm or less, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm), polystyrene particles (0.25 μm).
m) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic.

Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and petaine surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
12537 and 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present, and for miniaturization of the camera,
The diameter of the current 135 size 25 mm cartridge is 2
It is also effective to set it to 2 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are U.S. Pat. No. 4,834,306,
No. 5,226,613. Also, the so-called raw film before development and the developed photographic film may be stored in the same new cartridge or different cartridges.

The color photographic light-sensitive material of the present invention is also suitable as a color negative film for an advanced photo system (hereinafter referred to as APS), and NEXIA A, NEXIA manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film).
Films processed into APS format such as F, NEXIA H (in order, IS0 200/100/400) and stored in a special cartridge can be mentioned. These APS cartridge films are used by being mounted on an APS camera of the EPION series represented by the EPION 300Z manufactured by Fujifilm. Further, the color photographic light-sensitive material of the present invention,
This is a Fujicolor photo run made by Fujifilm. It is also suitable for films with lenses such as Super Slim.

The film photographed by the above is printed in the mini-lab system through the following steps.

(1) Acceptance (exposed cartridge film received from customer) (2) Detach step (transfer film from cartridge to intermediate cartridge for development step) (3) Film development (4) Rear touch step (development) (Return the used negative film to the original cartridge.) (5) Print (continuous automatic printing of C, H, P 3 type prints and index prints on color paper [preferably Fujifilm Super FA8]) (6) Collation , Shipping (collating cartridges and index prints with ID numbers and shipping with prints).

[0240] These systems include Fujifilm's Minilab Champion Super FA-298 / FA-278 / FA-258.
/ FA-238 is preferred. FP9 as a film processor
22AL / FP562B / FP562BL / FP362B / FP3622BL, and the recommended treatment chemical is Fujicolor Justit CN-16L.
PP3008AR / PP3008A / P as a printer processor
P1828AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A are listed, and the recommended treatment chemical is Fujicolor Justit CP
-47L. The detacher used in the detaching step and the rear toucher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The APS system can be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, Aladdin 1000 can be directly loaded with a developed APS cartridge film, or negative, positive, and print image information can be transferred to a 35mm film scanner FE.
-550 and PE-550 flat head scanner can be used to easily process and edit the obtained digital image data. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
The Aladdin 1000 also allows digital information to be stored directly on a floppy (registered trademark) disk or Zip disk, or via a CD-R (Compact Disc Recordab
le) can also be output.

On the other hand, at home, a photograph can be enjoyed on a TV simply by loading the developed APS cartridge film into the Fuji Film Photo Player AP-1, or by loading it into the Fuji Film Photo Scanner AS-1. It is also possible to continuously capture image information at high speed in a personal computer.
To input a film, print, or three-dimensional object to a personal computer, a Fuji Vision PhotoVision FV-10 / FV-5 can be used. Furthermore, image information recorded on a floppy disk, ZIP disk, CD-R or hard disk can be processed and enjoyed in various ways on a personal computer using the photo factory application software of FUJIFILM. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

To store the developed APS cartridge film, use Fuji Color Pocket Album AP-5 Pop
L, AP-1 pop L, AP-1 pop KG or cartridge file 16 is preferred.

[0244]

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

Example 1 Gelatin-1 to Gelatin-4 used as a dispersion medium in the following emulsion preparation and / or preparation of a coated sample are gelatins having the following attributes.

Gelatin-1: Normal alkali-treated ossein No. 1 extracted gelatin using bovine bone as a raw material. The molecular weight distribution measured by the PAGI method was such that the high molecular weight component was 2.5%.
% And low molecular weight components are 60.0%.

Gelatin-2: In an aqueous solution of gelatin-1,
A gelatin obtained by adding phthalic anhydride at 50 ° C. and a pH of 9.0 to cause a chemical reaction, removing residual phthalic acid, and drying. 95% of the -NH ₂ group in gelatin is chemically modified.

Gelatin-3: In an aqueous solution of gelatin-1,
Gelatin obtained by adding succinic anhydride under conditions of 50 ° C. and pH 9.0 to cause a chemical reaction, removing remaining succinic acid, and drying. 95% of the -NH ₂ group in gelatin is chemically modified.

Gelatin-4: In an aqueous solution of gelatin-1,
Reduce the molecular weight by the action of a degrading enzyme to reduce the average molecular weight to 1
After gelatinization, the enzyme was inactivated and gelatin was dried.

After the above gelatins 1 to 4 were all subjected to deionization treatment, the pH of a 5% aqueous solution at 35 ° C. was adjusted to 6.0.

(Preparation of Solid Fine Dispersion of Sensitizing Dye) Solid fine dispersions of sensitizing dyes-1 to 3 were prepared as follows. According to the conditions shown in Table 1, after dissolving the inorganic salt in ion-exchanged water, a sensitizing dye was added, and the mixture was dispersed at 2,000 rpm for 20 minutes using a dissolver blade at 60 ° C. to thereby sensitize. Solid fine dispersions of dyes-1 to 3 were prepared.

[0252]

[Table 1]

[0253]

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(Preparation of Emulsion 1-A) Low molecular weight gelatin
(Gelatin-4) Water solution containing 1.0 g and KBr 1.0 g
1200 mL of the liquid was kept at 35 ° C. and stirred. AgNO_Three
30 mL of an aqueous solution containing 1.9 g, containing 1.5 g of KBr
25 mL aqueous solution, low molecular weight gelatin (gelatin-4)
10 mL of aqueous solution containing 0.7 g by triple jet method
Nucleation by adding at a constant flow rate for 30 seconds
went. Add 5 g of KBr, heat to 75 ° C and ripen
Was. After aging process for 15 minutes after temperature rise, phthalation
35 g of gelatin (gelatin-2) was added. pH
Adjust to 5.6, AgNO_ThreeAqueous solution 150 containing 30 g
mL and KBr aqueous solution for 16 minutes by the double jet method.
Just added. At this time, the silver potential is applied to the saturated calomel electrode.
On the other hand, it was kept at 0 mV. Furthermore, AgNO_ThreeIncluding 110g
Aqueous solution and KBr aqueous solution containing 3.8 mol% KI (3
0% by weight) and the final flow rate is the initial flow rate
Over 15 minutes by accelerating the flow rate to 1.2 times
Was added. At this time, the silver potential was kept at 0 mV. Furthermore, A
gNO _Three132mL of aqueous solution containing 35g and KBr aqueous solution
Was added by the double jet method over 7 minutes. this
And KBr such that the potential at the end of the addition becomes +20 mV.
The addition of the aqueous solution was adjusted. After raising the temperature to 40 ° C, p-
Sodium iodoacetamidobenzenesulfonate
(Compound-1) was added in an amount of 7.1 g in terms of KI, and
Add 64 mL of 0.8 M aqueous sodium sulfite solution
Was. Further, the pH was raised to 9.0 by adding an aqueous NaOH solution.
After holding for 4 minutes to rapidly generate iodide ions, p
H was returned to 5.5. After returning the temperature to 75 ° C,
Sodium zhenthiosulfonate 2mg and additional zera
10 g of tin (gelatin-1) was added. After the addition,
0.001 wt% K_ThreeIrCl₆Add 10 mL of aqueous solution
And AgNO_Three250 mL of an aqueous solution containing 70 g
Added over 20 minutes. During the initial 6 minutes of addition, K
The silver potential was kept at -60 mV with an aqueous Br solution. Normal flow
After desalting by the curation method, the dispersed gelatin (ze
Ratin-1) 45 g was added, and the pH was adjusted to 40 at 40 ° C.
5. The pAg was adjusted to 8.7.

The temperature of the emulsion was raised to 56 ° C.
1-3 were added in the form of a fine solid dispersion in a molar ratio of 55: 40: 5 respectively. Then potassium thiocyanate,
Optimum chemical sensitization was performed by adding chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea. At the end of the chemical sensitization, the following compound-2 was added to prepare Emulsion 1-A.

The emulsion 1-A obtained had an equivalent sphere diameter of 0.86.
μm, average aspect ratio 6.5, average iodine content 4.3
Mole%.

[0257]

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(Preparation of Emulsion 1-B) In the preparation of Emulsion 1-A, the dispersed gelatin to be added after desalting was mixed with gelatin-5 (a mixture of the second extract and the third extract of gelatin-1) of the present invention. The molecular weight distribution measured by the PAGI method was 9.8% for high molecular weight components and 49.5% for low molecular weight components) except that emulsion 1 was changed to emulsion 1-A.
-B was produced.

(Preparation of Emulsion 1-C) In the preparation of Emulsion 1-A, dispersed gelatin added after desalting was mixed with gelatin-6 (mixture of extract No. 4 and extract No. 5 of gelatin-1) of the present invention. The molecular weight distribution measured by the PAGI method was 20.2% for the high molecular weight component and 38.9% for the low molecular weight component), except that emulsion 1-C was prepared in the same manner as emulsion 1-A. Produced.

(Preparation of Emulsion 1-D) In the preparation of Emulsion 1-A, the dispersion gelatin added after desalting was changed to Gelatin-7.
(Mixture of extract No. 6 and extract No. 7 of gelatin-1;
The molecular weight distribution measured by the PAGI method is such that the high molecular weight component is 32.0% and the low molecular weight component is 30.5%. )
Emulsion 1-D was prepared in the same manner as Emulsion 1-A, except that the composition was changed to

(Preparation of Emulsion 1-E) In the preparation of Emulsion 1-A, the dispersion gelatin added after desalting was changed to Gelatin-8.
(Gelatin-1 cross-linked with transglutaminase enzyme described in the detailed description; the molecular weight distribution measured by the PAGI method is 10.1% for high molecular weight components and 48.6% for low molecular weight components.) Emulsion 1-E was prepared in the same manner as Emulsion 1-A, except that the composition was changed to

(Preparation of Emulsion 1-F) In the preparation of Emulsion 1-A, the dispersed gelatin added after desalting was changed to Gelatin-9.
(Gelatin-1 is a crosslinking agent HI-1 described in the detailed description.
The molecular weight distribution measured by the PAGI method was 6.6% for the high molecular weight component and 4% for the low molecular weight component.
9.1%. Emulsion 1-F was prepared in the same manner as in Emulsion 1-A, except that the composition was changed to (1).

(Preparation of Emulsion 1-G) In the preparation of Emulsion 1-A, the dispersed gelatin added after desalting was changed to Gelatin-1.
0 (gelatin-1 was used as a crosslinking agent H-II-
Gelatin crosslinked with No. 4; the molecular weight distribution measured by the PAGI method is 11.8% for high molecular weight components and 42.5% for low molecular weight components. Emulsion 1-G was prepared in the same manner as in Emulsion 1-A except that the above was changed.

(Preparation of Emulsion 1-H) In the preparation of Emulsion 1-A, dispersed gelatin added after desalting was changed to Gelatin-1.
1 (gelatin-1 was used as a crosslinking agent H-VI-
Gelatin crosslinked in 3; the molecular weight distribution measured by the PAGI method is 8.2% for high molecular weight components and 48.2% for low molecular weight components. Emulsion 1-H was prepared in the same manner as in Emulsion 1-A, except that the composition was changed to (1).

(Preparation of Emulsion 1-I) In the preparation of Emulsion 1-A, the dispersed gelatin added after desalting was changed to Gelatin-1.
2 (gelatin-1 was used as a crosslinking agent H-VI-
Gelatin crosslinked in 3; the molecular weight distribution measured by the PAGI method is 26.0% for high molecular weight components and 34.7% for low molecular weight components. Emulsion 1-I was prepared in the same manner as in Emulsion 1-A, except that the composition was changed to (1).

(Preparation of Emulsion 1-J) In the preparation of Emulsion 1-A, the dispersed gelatin added after desalting was changed to Gelatin-1.
3 (gelatin-1 was used as a crosslinking agent H-VI-
Gelatin crosslinked with No. 3; the molecular weight distribution measured by the PAGI method is 34.3% for high molecular weight components and 29.9% for low molecular weight components. Emulsion 1-J was prepared in the same manner as in Emulsion 1-A, except that the composition was changed to (1).

(Preparation of Emulsion 1-K) In the preparation of Emulsion 1-A, the dispersed gelatin added after desalting was changed to Gelatin-1.
4 (gelatin obtained by crosslinking ordinary acid-treated ossein No. 1 extracted gelatin obtained from bovine bone with the crosslinking agent H-VI-3 described in the detailed description; the molecular weight distribution measured by the PAGI method is 12.4%, low molecular weight component 48.
3%. Emulsion 1-K was prepared in the same manner as Emulsion 1-A, except that the composition was changed to (1).

The emulsions 1-B to 1-K thus obtained all had an equivalent sphere diameter of 0.86 μm, an average aspect ratio of 6.5 and an average iodine content of 4.3 mol%.

(Evaluation of Emulsion Filtration Property) Emulsions 1-A to 1-K were evaluated for filtration property as follows.

[Filtration conditions] Filtration cross section: 3.14 cm ² Filtration temperature: 45 ° C. Filtration flow rate: 100 mL / min Filtration filter pore size: 5 μm Emulsions 1-A to 1-K were dissolved at 45 ° C. Filtration pressure change rate (value obtained by dividing the filtration pressure value 20 minutes after the start of filtration by the initial filtration pressure value immediately after the start of filtration: change rate = 1.0 (no change)
Is preferred. ) Was measured. The obtained results are shown in Table 2 below.

Next, on a cellulose triacetate film support provided with an undercoat layer, the above chemically sensitized emulsions 1-A to 1-K were provided with a protective layer under the following coating conditions. And application samples 101 to 111 were produced.

[Coating conditions] (1) Emulsion layer Emulsion: Various emulsions (silver 2.1 × 10 ^-2 mol / m ² ) Coupler: Compound 3 shown below (1.5 × 10 ^-3 mol / m)
² ) ・ tricresyl phosphate (1.1 g / m ² ) ・ gelatin-1 (2.3 g / m ² ) (2) protective layer ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt ( 0.08 g / m ² ) gelatin-1 (1.8 g / m ² ).

[0273]

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The obtained sample was allowed to stand at 40 ° C. and a relative humidity of 70% for 14 hours, then exposed for 1/100 second through a yellow filter and a continuous wedge, and subjected to the following color development processing.

[Color development] Process Processing time Processing temperature Color development 2 minutes 30 seconds 40 ° C. Bleaching and fixing 3 minutes 00 seconds 40 ° C. Rinse with water (1) 20 seconds 35 ° C. Rinse with water (2) 20 seconds 35 ° C. Stable 20 seconds 35 ℃ Drying 50 seconds 65 ℃.

Next, the composition of the processing solution will be shown. (Color development) (Unit g) 1-hydroxyethylidene-1,1-disulfone diethylenetriaminepentaacetic acid-1,1-disulfone 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyamine sulfate 2 0.4 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water was added to make 1.0 L pH 10.05.

(Bleach-fixing solution) (Unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 90.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Aqueous ammonium thiosulfate solution (70%) 260.0 mL Acetic acid (98%) 5.0 mL of the following compound-4 0.01 mol water was added to make 1.0 L pH 6.0.

[0278]

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(Washing solution) Tap water was mixed with H-type cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas),
Water is passed through a mixed-bed column filled with an OH-type anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by 20 mg / L of sodium diisocyanurate dichloride. And 1.5 g / L of sodium sulfate. This solution has a pH of 6.
It is in the range of 5-7.5.

(Stabilizing solution) (Unit: mg) Formalin (37%) 2.0 mL Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Water was added. 1.0 L pH 5.0-8.0.

The sensitivity of the freshness was represented by the relative value of the logarithm of the reciprocal of the exposure amount, which was expressed in lux seconds giving a density of fog + 0.2. In addition, the unexposed film of each sample
After storing at 0 ° C. and a relative humidity of 60% for 14 days, the storability was evaluated by measuring the sensitivity after performing the same exposure and development treatments. Table 2 shows the obtained results.

[0282]

[Table 2]

As shown in Table 2, in the emulsion using the gelatin of the present invention, the filterability of the emulsion alone was improved, and the sensitivity in freshness was further increased. This is considered to reflect the result of preventing aggregation of particles by the technique of the present invention. However, it can be seen that in an emulsion using gelatin in which the amount of the high molecular weight component was excessively increased, its filterability deteriorated, and the effect of sensitization was also reduced. In addition, it can be seen that the emulsion using the gelatin of the present invention is an emulsion excellent in storability with little decrease in sensitivity after storage. In particular, an emulsion using gelatin obtained by cross-linking alkali-treated gelatin with a cross-linking agent exhibits the best performance in both fresh sensitivity and sensitivity after storage.

Example 2 (Preparation of silver iodide fine grain emulsion) 1700 mL of an aqueous solution containing 0.23 g of KI and 23 g of low molecular weight gelatin (gelatin-4 described in Example 1) was stirred at 40 ° C. Ag
An aqueous solution containing 153 g of NO ₃ and an aqueous solution containing 149.5 g of KI were added over 13 minutes by the double jet method. After completion of the addition, the mixture was cooled to 40 ° C., desalted by a usual flocculation method, and 78 g of gelatin (gelatin-1 described in Example 1) was added to adjust the pH to 5.8 at 40 ° C. .

The obtained silver iodide fine grain emulsion was prepared in the following manner:
It contained 0.72 mol of Ag and 31 g of gelatin per gram, and had an average particle size of 0.03 μm and a coefficient of variation of 20%.

(Preparation of emulsion 2-A) 0.75 g of low molecular weight gelatin (gelatin-4 described in Example 1), KBr
An aqueous solution (1200 mL) containing 0.9 g and 0.2 g of denatured silicone oil (L7602 manufactured by Nippon Yunika Co., Ltd.) was maintained at 39 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred.
Aqueous solution containing 0.45 g of AgNO ₃ and 1.5 mol% of K
An aqueous KBr solution containing I was added by a double jet method over 16 seconds. At this time, the silver potential was kept at 0 mV with respect to the saturated calomel electrode (addition). Next, the temperature was raised to 54 ° C. to ripen. After ripening, 20 g of succinated gelatin (gelatin-3 described in Example 1) was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. Ag
288 mL of an aqueous solution containing 28.8 g of NO ₃ and an aqueous KBr solution were added over 53 minutes by a double jet method.
At this time, a silver iodide fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode (addition). ). After adding 2.5 g of KBr, Ag
An aqueous solution containing 87.7 g of NO ₃ and a KBr aqueous solution were added by a double jet method over a period of 63 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time,
The above silver iodide fine grain emulsion was prepared by adding silver iodide content of 10.5.
At the same time, the flow rate was accelerated so as to be mol%, and the silver potential was kept at -70 mV (addition). AgNO ₃ 4
132 mL of an aqueous solution containing 1.8 g and an aqueous KBr solution were added over 25 minutes by a double jet method. At this time,
The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV (addition). After adding 15 g of additional gelatin (gelatin-1 described in Example 1), the pH was adjusted to 7.3. Add KBr to reduce the silver potential to -70 m
After adjusting to V, 5.8 g of the above silver iodide fine grain emulsion was added in terms of KI weight. Immediately after the addition is completed, AgNO
609 mL of an aqueous solution containing 66.4 g of ₃ was added over 10 minutes. During the initial 6 minutes of the addition, the silver potential was kept at -70 mV with an aqueous KBr solution (addition). After desalting by a usual flocculation method, 40 g of dispersed gelatin (gelatin-1 described in Example 1) was added, and the pH was adjusted to 6.5 and the pAg to 8.2 at 40 ° C.

After adding the following compound-5 and compound-6, the temperature was raised to 56 ° C. After the silver iodide fine grain emulsion was added in an amount of 4.5 × 10 ⁻⁴ mol per mol of silver, the following sensitizing dyes ⁴ , 5, 6, and 7 were added. Further, potassium thiocyanate, chloroauric acid, sodium thiosulfate,
N, N-dimethylselenourea was added for optimal chemical sensitization. Compound-7 and Compound-8 at the end of chemical sensitization
Was added.

The obtained emulsion 2-A had an equivalent circle diameter of 1.42.
μm, the average aspect ratio was 7.2, and the average iodine content was 7 mol%. This emulsion was prepared at a liquid nitrogen temperature of 200
According to observation with a kV transmission electron microscope, an average of 10 or more dislocation lines per grain were present near the outer periphery of the tabular grains.

(Preparation of Emulsion 2-B) In the preparation of Emulsion 2-A, 1.5 mg of thiourea dioxide was added immediately before the addition, and 2 mg of sodium benzenethiosulfonate was added after the addition was completed. Was formed in the same manner as in Emulsion 2-A except that Emulsion 2-B was formed on the grain surface.
Was prepared. Emulsion 2-B obtained had a circle equivalent diameter of 1.42.
μm, the average aspect ratio was 7.2, and the average iodine content was 7 mol%.

(Preparation of Emulsion 2-C) Emulsion 2-C was prepared in the same manner as in Emulsion 2-B, except that the addition and the added silver potential were changed to -25 mV in the preparation of Emulsion 2-B. The obtained emulsion 2-C had an equivalent circle diameter of 1.64 μm,
The average aspect ratio was 10.9, and the average iodine content was 7 mol%.

(Preparation of Emulsion 2-D) Emulsion 2-D was prepared in the same manner as in Emulsion 2-B, except that the addition and the added silver potential were changed to -60 mV in the preparation of Emulsion 2-B. The resulting emulsion 2-D had a circle-equivalent diameter of 2.02 μm,
The average aspect ratio was 20.0, and the average iodine content was 7 mol%.

(Preparation of Emulsion 2-E) In the preparation of Emulsion 2-A, additional gelatin and dispersed gelatin were added to gelatin-10 described in Example 1 (gelatin-1 described in Example 1 Gelatin cross-linked by the cross-linking agent H-II-4 described in the description; the molecular weight distribution measured by the PAGI method is 11.8% for high molecular weight components and 42.% for low molecular weight components.
5%. Emulsion 2-E was prepared in the same manner as in Emulsion 2-A, except that the composition was changed to (2). Emulsion 2-E obtained had an equivalent circle diameter of 1.42 μm, an average aspect ratio of 7.2, and an average iodine content of 7 mol%.

(Preparation of Emulsion 2-F) Emulsion 2-F was prepared in the same manner as in Emulsion 2-B, except that the additional gelatin and the dispersed gelatin were changed to the above-mentioned gelatin-10 in the preparation of Emulsion 2-B. Produced. The obtained emulsion 2-F had an equivalent circle diameter of 1.42 μm, an average aspect ratio of 7.2, and an average iodine content of 7 mol%.

(Preparation of Emulsion 2-G) Emulsion 2-G was prepared in the same manner as in Emulsion 2-C, except that the additional gelatin and the dispersed gelatin were changed to the above-mentioned gelatin-10 in the preparation of Emulsion 2-C. did. The obtained emulsion 2-G had an equivalent circle diameter of 1.64 μm, an average aspect ratio of 10.9, and an average iodine content of 7 mol%.

(Preparation of Emulsion 2-H) Emulsion 2-H was prepared in the same manner as Emulsion 2-D, except that the additional gelatin and the dispersed gelatin were changed to the above-mentioned gelatin-10 in the preparation of Emulsion 2-D. Produced. The obtained emulsion 2-H had an equivalent circle diameter of 2.02 μm, an average aspect ratio of 20.0, and an average iodine content of 7 mol%.

Emulsions 2-A to 2-
H was applied in the same manner as in Example 1 except that 1.1 × 10 ⁻⁴ mol / m ^{2 of the following} compound-9 was added to the emulsion layer to prepare coating samples 201 to 208. . Further, each of the emulsions 2-A to 2-H was dissolved at 40 ° C,
After a lapse of 8 hours, coating was performed in the same manner as described above to prepare coated samples 211 to 218.

[0297]

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[0298]

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The obtained sample was allowed to stand at 40 ° C. and a relative humidity of 70% for 14 hours, exposed to light for 1/100 second through a yellow filter and a continuous wedge, and subjected to the same color development processing as in Example 1.

The sensitivity was represented by the relative value of the logarithm of the reciprocal of the exposure amount expressed in lux.sec giving a density of fog + 0.2. The RMS granularity of each sample at a density of fog + 0.2 was measured. Further, for samples 201 to 208,
After preserving each unexposed film at 50 ° C. and a relative humidity of 60% for 14 days, the same exposure and development treatments were performed, and the change in fog density was measured to evaluate the preservability.
Table 3 shows the obtained results.

[0301]

[Table 3]

As shown in Table 3, it can be seen that the emulsion using the gelatin of the present invention has a high fresh sensitivity and is excellent in the granularity represented by the RMS value. In the combination with the hole trap zone, the emulsion using conventional gelatin was sensitized, but at the same time, the storage properties represented by the change in graininess and fog density were deteriorated. In addition, the sensitivity is increased by increasing the aspect ratio of the particles, but the storage stability is similarly deteriorated. An emulsion using the gelatin of the present invention has high sensitivity and excellent storage stability even in combination with a hole trap zone or a high aspect ratio.
Furthermore, it can be seen that the emulsion using the gelatin of the present invention does not deteriorate its performance even after coating with the lapse of time of dissolution, and has excellent suitability for production.

Example 3 (Preparation of Tabular Seed Emulsion) 1500 mL of an aqueous solution containing 1.0 g of low molecular weight gelatin (gelatin-4 described in Example 1) and 1.2 g of KBr was stirred at 40 ° C. AgNO
_{3 An} aqueous solution containing 12 g and an aqueous solution containing 8.5 g of KBr,
Further, low molecular weight gelatin (the gelatin described in Example 1)
4) An aqueous solution containing 1.7 g was subjected to 60
Added over seconds. After adding an aqueous solution containing 1.44 g of KBr, the temperature was raised to 50 ° C. After the temperature was increased and stirring was continued for 30 minutes, an aqueous solution containing 2.1 g of AgNO ₃ was added, 0.05 mol of ammonia was added, and after aging, p was added with acetic acid.
H was adjusted to 5.0. Next, an aqueous solution containing 208 g of AgNO ₃ and an aqueous KBr solution were subjected to a double jet method at a flow rate of 60 while maintaining the pAg in the solution at 9.0.
Added over minutes. After completion of the addition, the mixture was cooled to 40 ° C., desalted by a usual flocculation method, 50 g of dispersed gelatin (gelatin-1 described in Example 1) was added, and the pH was adjusted to 5.8 and pAg at 40 ° C. Was adjusted to 8.8.

The seed emulsion was tabular grains having an equivalent circle diameter of 0.67 μm and an average aspect ratio of 7.0.

(Preparation of Emulsion 3-A) 1200 mL of an aqueous solution containing 3.0 g of KBr and 40 g of gelatin (gelatin-1 described in Example 1) was stirred at 78 ° C. After adding 23.6 g of the above-mentioned tabular seed emulsion, AgNO ₃ .
Aqueous solution containing 7 g, 18.0 g of KBr and KI 0.4
while maintaining the pAg in the solution at 8.2, the flow rate was accelerated by the double jet method so that the final flow rate was 1.5 times the initial flow rate, and added over 80 minutes. Further, an aqueous solution containing 127 g of AgNO ₃ and KBr
An aqueous solution containing 87 g and 12 g of KI
While maintaining g at 8.2, the flow rate was accelerated by the double jet method so that the final flow rate was 1.5 times the initial flow rate, and 120
After adding over 2 minutes, an aqueous solution containing 22.6 g of AgNO ₃ and an aqueous solution containing 15.9 g of KBr were added to the p solution in the solution.
The Ag was added at a constant flow rate over 12 minutes while maintaining the Ag at 8.0. Thereafter, the pAg is adjusted to 9.
After stirring at 1 for 1 minute, 23.6 g of the silver iodide fine grain emulsion described in Example 2 was rapidly added, followed by stirring for 1 minute. An aqueous solution containing 44.7 g of AgNO ₃ was added at a constant rate over a period of 20 minutes. After desalting by the usual flocculation method, 60 g of dispersed gelatin (gelatin-1 described in Example 1) was added, and the pH was adjusted to 5.8 and the pAg was adjusted to 8.8 at 40 ° C.

Next, the temperature was raised to 56 ° C., and the sensitizing dye ExS-9, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea described below were added to optimize the chemical reaction. I was sensitized. At the end of chemical sensitization, compound-8 described in Example 2 was added.

The obtained emulsion 3-A was tabular grains having an average particle diameter (equivalent spherical diameter) of 1.40 μm, an equivalent circular diameter of 2.80 μm, an average aspect ratio of 12.0, and an average iodine content of 6.4 mol%. Met.

(Preparation of Emulsion 3-B) In the preparation of Emulsion 3-A, the dispersion gelatin was changed to the gelatin-1 described in Example 1.
0 (gelatin-1 was used as a crosslinking agent H-II-
Gelatin crosslinked with No. 4; the molecular weight distribution measured by the PAGI method is 11.8% for high molecular weight components and 42.5% for low molecular weight components. Emulsion 3-B was prepared in the same manner as Emulsion 3-A, except that the above conditions were changed.

(Preparation of Emulsion 3-C) In the preparation of Emulsion 3-A, the dispersed gelatin was changed to Gelatin-11 (Gelatin-1).
Is a gelatin cross-linked with a cross-linking agent H-VI-3 described in the detailed description; the molecular weight distribution measured by the PAGI method is 8.2% for a high molecular weight component and 48.2% for a low molecular weight component. )) Except that emulsion 3 was changed in the same manner as emulsion 3-A.
-C was produced.

(Preparation of Emulsion 3-D) In the preparation of Emulsion 3-A, immediately after adding the tabular seed emulsion, 1.5 × 10 ⁻⁵ mol of thiourea dioxide and 1.0 mol of sodium benzenethiosulfonate were added. Emulsion 3-D was prepared in the same manner as Emulsion 3-A, except that a hole trap zone was formed inside the grains by adding × 10 ^-5 mol.

(Preparation of Emulsion 3-E) In the preparation of Emulsion 3-B, immediately after adding the tabular seed emulsion, 1.5 × 10 ⁻⁵ mol of thiourea dioxide and 1.0% of sodium benzenethiosulfonate were added. Emulsion 3-E was prepared in the same manner as Emulsion 3-B, except that a hole trap zone was formed inside the grains by adding ^10-5 mol.

(Preparation of Emulsion 3-F) In the preparation of Emulsion 3-C, immediately after adding the tabular seed emulsion, 1.5 × 10 ⁻⁵ mol of thiourea dioxide and 1.0% of sodium benzenethiosulfonate were added. Emulsion 3-F was prepared in the same manner as Emulsion 3-C, except that a hole trapping zone was formed inside the grains by adding × 10 ^-5 mol.

As described above, all of the obtained emulsions 3-B to 3-F had an equivalent sphere diameter of 1.40 μm, an equivalent circle diameter of 2.80 μm, an average aspect ratio of 12.0, and an average iodine content of 6.4 mol%. .

(Support) The support used in this example was prepared by the following method. 100 parts by weight of a polyethylene-2,6-naphthalate (hereinafter referred to as PEN) polymer and Tinuvin P. as an ultraviolet absorber. 326
2 parts by weight (Ciba-Geigy) were dried, melted at 300 ° C., extruded from a T-die, and longitudinally stretched 3.3 times at 140 ° C.
The film is stretched 3.3 times at 30 ° C. and further stretched at 250 ° C. for 6 times.
It was heat-set for 2 seconds to obtain a 90 μm thick PEN film.
The PEN film has a blue dye, a magenta dye and a yellow dye (public technique: official technique No. 94-602).
No. 3, I-1, I-4, I-6, I-24, I-2
6, I-27, II-5) was added in an appropriate amount. Furthermore, it is wound around a stainless steel core having a diameter of 20 cm, and
A heat history of 48 ° C. for 48 hours was given to make the support less likely to have curl.

(Coating of Undercoat Layer) The support was subjected to a corona discharge treatment, a UV discharge treatment and a glow discharge treatment on both surfaces, and then gelatin was applied to each surface at 0.1 g / m ² ,
Sodium-α-sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² ,
p-chlorophenol 0.2 g / m ² , (CH ₂ ＣＨCHS
O ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² ,
Polyamide-epichlorohydrin polycondensate 0.02 g /
An undercoat solution of m ² was applied (10 mL / m ² , using a bar coater), and an undercoat layer was provided on the high temperature side during stretching. 115 for drying
6 ° C. for 6 minutes (all rollers and transport devices in the drying zone are at 115 ° C.).

(Coating of Back Layer) The following antistatic layer, magnetic recording layer and sliding layer were coated as back layers on one side of the support after undercoating.

(Coating of antistatic layer) Average particle size 0.005
The specific resistance of tin oxide-antimony oxide composite of μm is 5Ω
Cm particle dispersion (secondary aggregate particle size of about 0.0
8 μm), 0.2 g / m ² , gelatin 0.05 g / m ² ,
(CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.0
2 g / m ² , poly (degree of polymerization 10) oxyethylene-p-
Coated with 0.005 g / m ^{2 of} nonylphenol and resorcinol.

(Coating of Magnetic Recording Layer) 3-Poly (degree of polymerization 1)
5) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am ² / Kg, Fe ^{+ 2} / F
e ⁺³ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06 g / m ² and diacetyl cellulose 1.2 g / m ² (iron oxide is dispersed in an open kneader And a sand mill), and C was used as a curing agent.
_{2 H 5 C (CH 2 OCONH} -C 6 H 3 (CH 3) NCO) 3
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a 1.2 μm-thick magnetic recording layer. Silica particles (0.3 μm) and 3-poly (degree of polymerization 15) as matting agents
Abrasive aluminum oxide (0.15 μm) coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) was added at a concentration of 10 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). X- light (blue filter) saturation magnetization moment of about 0.1, and the magnetic recording layer is color density increment of D ^B of the magnetic recording layer of the 4.2Am ² / kg, a coercive force 7.3 × 10 ⁴ A / m,
The squareness ratio was 65%.

(Application of Sliding Layer) Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ CO
OC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O
A mixture of (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) was applied. This mixture was melted at 105 ° C. in xylene / propylene monomethyl ether (1/1), and propylene monomethyl ether (10-fold amount) was added at room temperature.
And then dispersed in acetone (average particle size: 0.01 μm) and then added. Aluminum oxide (0.15%) coated with silica particles (0.3 μm) as a matting agent and 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by weight) as an abrasive
μm) was added so as to be 15 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless steel hard sphere, load 100
g, speed 6 cm / min), a coefficient of static friction of 0.07 (clip method), and a coefficient of kinetic friction between an emulsion surface and a sliding layer, which will be described later, were 0.12.

(Preparation of Multi-Layer Coated Sample) Next, on the opposite side of the back layer obtained above, each layer having the following composition was simultaneously multi-layer coated to obtain a multi-layer color photosensitive material sample 3.
01 to 306 were prepared. Sample 301 to Sample 30
Emulsions 3-A to 3-F were used for the twelfth layer of No. 6 respectively. Furthermore, except that the magnetic recording layer of the back layer was removed, the sample 311 was manufactured in the same manner as in the production of the samples 301 to 306.
~ Sample 316 was produced.

(Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: organic solvent of high boiling store ExY: yellow Coupler H: gelatin hardener ExS: sensitizing dye.

The number corresponding to each component indicates the coating amount expressed in g / m ² , and the amount of silver halide indicates the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.03 Solid Disperse Dye ExF-3 0.04 HBS-1 0.15 HBS-2 0.02.

Second layer (intermediate layer) Silver iodobromide emulsion M silver 0.065 ExC-2 0.04 polyethyl acrylate latex 0.20 gelatin 1.04.

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.03 ExC-4 0.10 ExC-5 0.02 ExC-6 0.01 Cpd-2 0.025 HBS-1 0.10 gelatin 0.80.

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.68 ExS-1 4.5 × 10 ^-4 ExS-2 1.1 × 10 ^-5 ExS-3 2.3 × 10 ^-4 ExC-1 0.13 ExC-2 0.06 ExC-3 0.007 ExC-4 0.09 ExC-5 0.015 ExC-6 0.007 Cpd-2 0.023 HBS-10 .10 gelatin 0.75.

Fifth Layer (High Sensitive Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 1.60 ExS-1 4.7 × 10 ^-4 ExS-2 1.5 × 10 ^-5 ExS-3 2.8 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.02 ExC-7 0.01 Cpd-2 0.05 HBS-1 0.22 HBS-2 0.05 Gelatin 1.10 .

Sixth layer (intermediate layer) Cpd-1 0.09 Solid disperse dye ExF-4 0.03 HBS-1 0.05 Polyethyl acrylate latex 0.15 Gelatin 1.10.

Seventh Layer (Layer that Gives Layered Effect to Red Sensitive Layer) Silver Iodobromide Emulsion 0.56 ExS-4 1.7 × 10 ^-4 ExS-5 4.6 × 10 ^-4 Cpd-4 0.03 ExM-2 0.096 ExC-9 0.021 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Eighth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion F silver 0.15 silver iodobromide emulsion G silver 0.10 silver iodobromide emulsion H silver 0.40 ExS-6 3.7 × 10 ^-4 ExS-7 2.6 × 10 ^-4 ExS-8 9.8 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS- 3 0.01 gelatin 0.73.

Ninth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 0.83 ExS-6 1.1 × 10 ^-4 ExS-7 3.2 × 10 ^-4 ExS-8 1.2 × 10 ^-3 ExC-8 0.01 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.01 ExY-5 0.04 HBS-1 0.13 HBS-34 .0 × 10 ^-3 gelatin 0.80.

Tenth Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion J Silver 0.99 ExS-6 1.0 × 10 ^-4 ExS-7 1.1 × 10 ^-4 ExS-8 7.2 × 10 ^-4 ExC-1 0.01 ExM-1 0.02 ExM-4 0.025 ExM-5 0.014 Cpd-3 0.04 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1. 33.

Eleventh Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.015 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.01 Solid Disperse Dye ExF-6 0.01 Oil-soluble Dye ExF-7 02 solid disperse dye ExF-8 0.01 HBS-1 0.15 gelatin 0.66.

12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K silver 0.12 Silver iodobromide emulsion L silver 0.49 ExS-9 9.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.05 ExY-2 0.22 ExY-3 0.50 ExY-4 0.02 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20.

Thirteenth Layer (High Sensitive Blue Sensitive Emulsion Layer) Emulsions shown in Table 5 Silver 1.30 ExS-9 5.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0. 01 Cpd-2 0.10 Cpd-3 1.0 × 10 ⁻³ HBS-1 0.07 Gelatin 0.70.

Fourteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 UV-4 0.025 HBS-1 5.0 × 10 ^-2 HBS-4 5 0.0 × 10 ^-2 gelatin 1.8.

Fifteenth layer (second protective layer) Silver iodobromide emulsion M silver 0.10 H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (diameter 1) 0.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70.

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-5, B-4 to B -6, F-1 to F
-18 and iron, lead, gold, platinum, palladium, iridium and rhodium salts.

The average A of the emulsions A to M used in the preparation of each sample
The gI content and particle size are shown in Table 4.

[0340]

[Table 4]

In Table 4, (1) Emulsions A to L were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to L are described in JP-A-3-23745.
According to the example of No. 0, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer.

(3) Preparation of tabular grains is disclosed in
According to the example of 58 426, low molecular weight gelatin is used.

(4) Tabular grains are disclosed in JP-A-3-2374.
Dislocation lines as described in No. 50 have been observed using a high voltage electron microscope.

(Preparation of Dispersion of Organic Solid Disperse Dye) The following ExF-2 was dispersed by the following method. That is, water 21.7
mL and a 5% aqueous solution of sodium p-octylphenoxyethoxyethanesulfonic acid 3 mL and a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 1
0) 0.5 g was placed in a 700 mL pocket mill, 5.0 g of dye ExF-2 and 500 mL of zirconium oxide beads (1 mm in diameter) were added, and the contents were dispersed for 2 hours.
For this dispersion, a B0 type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, 8 g of a 12.5% gelatin aqueous solution was added, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44μ
m.

Similarly, ExF-3, ExF-4, E
A solid dispersion of xF-6 and ExF-8 was obtained. The average particle diameter of the fine dye particles is 0.24 μm and 0.45 μm, respectively.
m, 0.52 μm and 0.25 μm. ExF
-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.

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[0362]

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The samples 301 to 30 thus manufactured
6 and Samples 311 to 316 were allowed to stand for 14 hours under the condition of 40 ° C. and 70% relative humidity, and then subjected to sensitometric exposure for 1/100 second through a continuous wedge at a color temperature of 4800 K to perform the following color development processing. .

The processing method is described below.

[Color development processing] Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 15 seconds 38 ° C. 33 mL 20 L Bleaching 6 minutes 30 seconds 38 ° C. 25 mL 40 L Rinse water 2 minutes 10 seconds 24 ° C. 1200 mL 20 L 4 minutes 20 seconds 38 ° C 25mL 30L water washing (1) 1 minute 05 seconds 24 ° C To (2)-(1) 10L countercurrent piping system water washing (2) 1 minute 00 seconds 24 ° C 1200mL 10L water washing (3) 1 minute 05 seconds 38 ° C 25 mL 10 L Drying 4 minutes 20 seconds 55 ° C * The replenishment amount is 35 mm wide and 1 m long.

Next, the composition of the processing solution will be described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-3.0 3.2 1,1-diphosphonic acid Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg --- Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-4.5 5.5. 5 Hydroxyethylamino] -2-methylaniline sulfate Water was added to 1.0 1.0 L pH 10.05 10.10.

(Bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sec. 100.0 120.0 Sodium iron trihydrate Ethylenediamontetraacetic acid dina 10.0 11.0 Thorium salt Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Aqueous ammonia (27%) 6.5 mL 4.0 mL Add water 1.0 L 1.0 L pH 6.0 5.7.

(Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 0.5 0.7 Sodium salt Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 An aqueous solution of ammonium thiosulfate (70% 170.0 mL 200.0 mL Water was added to make 1.0 L 1.0 L pH 6.7 6.6.

(Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.00 mL 3.0 mL Polyoxyethylene-p-mono 0.3 0.45 Nonylphenyl ether (Average degree of polymerization 10) Ethylenediamine 1.0 L 1.0 L pH 5.8-8.0 5.8-8.0 by adding water tetrasodium di-0.05 0.08 sodium salt

The sensitivity was represented by the relative value of the logarithm of the reciprocal of the exposure amount expressed in lux.sec giving a yellow density of fog + 0.2. Further, the RMS granularity of each sample at a yellow density of fog + 0.2 was measured.

Next, each sample was cut into a size of 24 mm and a width of 160 cm.
And a perforation provided at 32 mm intervals, and subjected to sensitometric exposure for 1/100 second through a continuous wedge at a color temperature of 4800 K, and then to FIG. 1 of US Pat. No. 5,296,887. ~ FIG.
And stored in a film cartridge described in (1). After storing the film cartridge containing each sample at 50 ° C. for 60 days at a relative humidity of 60%, perform the above-described development treatment to measure the yellow relative sensitivity at fog + 0.2 and the change in yellow fog density before and after storage. Was used to evaluate the storage stability. Table 5 shows the obtained results.

[0372]

[Table 5]

As shown in Table 5, the light-sensitive material using the emulsion containing gelatin of the present invention was excellent in fresh sensitivity and granularity, and also excellent in sensitivity and fog fluctuation after storage of a latent image. I understand. Further, the emulsion containing the gelatin of the present invention may be used in a hole trap zone or an AP.
It has been clarified that excellent storage performance is exhibited even in combination with the magnetic recording layer which is an essential element as an S-sensitive material.

Continued on the front page (72) Inventor Hiroyuki Kawamoto 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H023 BA04 CB02 CB06 CB07 DB05 FA09 HA04

Claims (8)

[Claims] 1. A photosensitive silver halide emulsion containing silver halide grains, characterized by containing gelatin satisfying requirement (a). (A) In the molecular weight distribution of the gelatin measured according to the PAGI method, the high molecular weight component having a molecular weight of about 2,000,000 or more is 5% to 30%, and the low molecular weight component having a molecular weight of about 100,000 or less is 55% or less. In range. 2. The light-sensitive silver halide emulsion according to claim 1, comprising gelatin satisfying the requirement (b). (B) In the molecular weight distribution of the gelatin measured according to the PAGI method, the high molecular weight component having a molecular weight of about 2,000,000 or more is 5% to 15%, and the low molecular weight component having a molecular weight of about 100,000 or less is 50% or less. In range. 3. The photosensitive silver halide emulsion according to claim 1, wherein the emulsion contains gelatin satisfying the requirement (c). (C) The gelatin is a soluble gelatin crosslinked with a crosslinking agent. 4. The photosensitive silver halide emulsion according to claim 1, wherein the emulsion contains gelatin satisfying the requirement (d). (D) a soluble alkali treatment in which the gelatin is crosslinked using at least one crosslinking agent selected from the group consisting of s-triazine compounds, vinylsulfone compounds, carbamoylammonium salts and carbodiimide compounds as crosslinking agents. It is gelatin. 5. The photosensitive silver halide emulsion according to claim 1, wherein the emulsion has a hole trap zone in at least one of the inside and the surface of the silver halide grain. 6. The total projected area of the silver halide grains is 60.
The photosensitive silver halide emulsion according to any one of claims 1 to 5, wherein at least% of the emulsion is occupied by tabular silver halide grains having an aspect ratio of 8.0 or more. 7. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the light-sensitive silver halide emulsion layer has at least one light-sensitive silver halide emulsion layer.
A silver halide photographic light-sensitive material comprising the light-sensitive silver halide emulsion according to any one of the above. 8. The silver halide photographic material according to claim 7, further comprising a magnetic recording layer containing magnetic particles on the back surface opposite to the support.