JP2001228573A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material free from defective conveyance due to the deterioration of the material of suckers for conveyance and the sticking of a fallen matting agent to the suckers even in the long-term use of various automatic conveyance systems for a silver halide photographic sensitive material and also free of the deterioration of its scuffing resistance. SOLUTION: Relating to the silver halide photographic sensitive material with at least one photosensitive sliver halide emulsion laver on at least one side of the base, a matting agent and an antifoggant are contained in the at least one emulsion layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material suitable for various automatic conveying devices for silver halide photographic light-sensitive materials.

[0002]

2. Description of the Related Art Silver halide photographic materials are often conveyed by various automatic conveying devices. Medical photosensitive materials are also conveyed by various automatic conveyance devices such as a receive supplier, an automatic developing machine with an auto feeder, a chest changer, and an imager. Adhesion to the suction cup causes a transportation failure, which is a problem.

[0003] Usually, a matting agent is added to the surface protective layer.
It has been found that the addition of a layer other than the surface protective layer such as a silver halide emulsion layer (hereinafter, also referred to as an emulsion layer) has an effect of preventing peeling off. There was a problem with deterioration of the resistance.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for transporting a silver halide photographic material even if the automatic transport apparatus is used for a long time. It is an object of the present invention to provide a silver halide photographic light-sensitive material which does not cause a conveyance failure due to a deterioration of a sucker material or a matting agent that has fallen off and adheres to the sucker, and is not accompanied by deterioration of scratch resistance.

[0005]

The above object of the present invention is achieved by the following constitution.

[0006] 1. In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on at least one side on a support, at least one of the emulsion layers
A silver halide photographic material comprising a layer containing a matting agent and an antifoggant.

[0007] 2. 2. The silver halide photograph according to 1, wherein the fog inhibitor is a mercapto compound represented by the general formula (1), an aryliodonium compound or a disulfide compound represented by the general formula (2). Photosensitive material.

[0008] 3. In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on at least one side on a support, at least one of the emulsion layers
A silver halide photographic light-sensitive material characterized in that the layer contains a matting agent in the emulsion layer and the matting agent has a glass transition point of from 40 ° C to 90 ° C.

4. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side on a support and containing a matting agent, the total of the hydrophilic colloid layers on the side having the emulsion layer The film thickness is 3.5
μm, the particle size of the matting agent is 1.1 to 2.0 times the total thickness of the hydrophilic colloid layer, and the center of gravity of the matting agent is in the hydrophilic colloid layer. A silver halide photographic light-sensitive material, characterized in that the ratio of the number of matting agents is 50% or more.

That is, a layer other than the surface protective layer (mainly an emulsion layer)
When a matting agent is added to the composition, it contains an antifoggant (preferably an antifoggant such as a compound represented by the general formula (1), a compound represented by the general formula (2) or a disulfide compound); It has been found that by setting the glass transition point of the matting agent to 40 ° C. or more and 90 ° C. or less, deterioration of scratch resistance can be suppressed.

The photosensitive material has a dry film thickness of 3.5 μm.
And the particle size of the matting agent is 1.1 to 2.0 times the layer thickness of the hydrophilic colloid layer, and the center of gravity of the matting agent is located in the hydrophilic colloid layer. The present invention has been achieved by finding that the matting agent can be prevented from falling off when the ratio of the number of the matting agents is 50% or more.

Hereinafter, the present invention will be described in detail. The mercaptoazoles, which are the mercapto compounds represented by the general formula (1) of the present invention used in the present invention, will be described.

In the general formula (1), Z is
N- or ＣC (X)-(X represents an alkyl group or an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl group or an aryl group having a hydrophilic group.

An alkyl group represented by X, Y and M,
The aryl group and the ammonium group include those having a substituent.

Preferred among the alkyl and aryl groups represented by X are alkyl groups having 1 to 30 carbon atoms, phenyl groups having 6 to 30 carbon atoms, and naphthyl groups having 10 to 30 carbon atoms. is there. These also include those having a substituent.

Among the alkyl groups and aryl groups represented by Y, preferred are alkyl groups having 1 to 30 carbon atoms and aryl groups having 6 to 30 carbon atoms, and particularly preferred are those having 6 to 30 carbon atoms. It is a phenyl group or a naphthyl group having 10 to 30 carbon atoms. These also include those having a substituent. In the above, the substituent is not particularly limited, for example, a hydroxy group, a carboxyl group,
Examples include a sulfo group, an alkoxy group, an aminocarbonyl group, an acylamino group, and a ureido group.

M represents a hydrogen atom, a metal atom or ammonium, but represents a hydrogen atom, an alkali metal atom or quaternary ammonium.

Hereinafter, specific examples of the mercapto compound represented by the general formula (1) are shown, but the present invention is not limited thereto.

[0019]

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[0020]

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The mercapto compound represented by the general formula (1) can be easily synthesized by using isothiocyanate as a starting material, as is generally well known. The patents and literature examples in which reference synthesis methods are described are shown below. US Patent No. 2,58
5,388, 2,541,924, Tokiko 42
No. 21842, JP-A-53-50169, British Patent No. 1,275,701; A. Berges et
all "Journal of Heterocycll
ic Chemistry ", Vol. 15, page 981 (197
8 years), "The Chemistry of Hete
rocyclic Chemistry "Imidaz
ole and Derivatives part
I. Pp. 336-339 Chemical Abstra
ct 58, 7921 (1963) p. 394; H
oggarth “Journal of Chemical
al Society "1949 1116-116
7 and S.P. R. Sandler, W.C. "O" by Karo
rgic Functional GroupPr
evolutions "Academic Press
Pp. 312-315, published in 1968.

These compounds are photographic emulsions or constituent layers other than emulsion layers (for example, an overcoat layer, a filter layer, an intermediate layer, etc.) as an aqueous solution, a hydrochloric acid aqueous solution or a methanol solution, and a layer adjacent to the emulsion layer is preferred. ) Is added to the hydrophilic colloid solution. The timing of addition is not particularly limited, but when it is added to a photographic emulsion, it is convenient to add it during the second ripening and immediately before coating. These compounds are used in an amount of 0.3 to 5 mmol, preferably 0.5 to 2 mmol, per 1 mol of silver.

Next, the aryliodonium compound represented by the general formula (2) of the present invention used in the present invention will be described.

In the general formula (2), R₁, R_TwoAnd
And R_ThreeIs suitable for use in silver halide photographic elements.
Activity of aryl iodonium compounds
Is a substituent that does not interfere with the properties. R₁, R_TwoAnd R_ThreeIs each
A hydrogen atom, or a substituted or unsubstituted aliphatic group,
An aromatic or heterocyclic group, or R₁, R_TwoYou
And R_ThreeAny two of them together have 5 or 6 members
It may form a ring or multiple rings. R₁, R_TwoAnd R_Three
Represents an alkoxy group (eg, methoxy group, ethoxy group)
Group, octyloxy group, etc.), hydroxy group, halogen source
And an aryloxy group (for example, phenoxy group, tolyl
Oxy group, etc.), alkylthio group (for example, methylthio
Group, butylthio group), arylthio group (for example,
An acyl group (e.g., acetyl group,
Pionyl, butyryl, valeryl, etc.), sulfonyl
Groups (eg, methylsulfonyl, phenylsulfonyl
Group), acyloxy group (for example, acetoxy group,
Zooxy group, etc.), carboxyl group, cyano group, nitro
Group, sulfo group, alkylsulfoxide group and trifur
It may be an oloalkyl group. In a preferred embodiment,
And R₁, R_TwoAnd R _ThreeIs a hydrogen atom, an aliphatic
Group, aromatic group or heterocyclic group. Another preferred implementation
In embodiments, R₁And R_TwoAre a hydrogen atom and a halogen
Atom, an aliphatic group, an aromatic group or a heterocyclic group; and
R_ThreeIs a sulfo group or a carboxyl group.

The aliphatic groups represented by R ₁ , R ₂ and R ₃ are preferably alkyl groups having 1 to 22 carbon atoms, or alkenyl or alkynyl groups having 2 to 22 carbon atoms. More preferably, they have 1 to 1 carbon atoms.
It is an alkyl group having 10 or an alkenyl or alkynyl group having 3 to 5 carbon atoms. Most preferably, they are alkyl groups of 1 to 5 carbon atoms. These groups may or may not have a substituent. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl,
Examples include a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, isopropyl, and t-butyl. Examples of the alkenyl group include an allyl group and butenyl, and examples of the alkynyl group include a propargyl group and butynyl.

Aromatic groups include aromatic groups preferably having 6 to 20 carbon atoms, especially phenyl and naphthyl groups. More preferred is an aromatic group having 6 to 10 carbon atoms, most preferably the aromatic group is phenyl. These groups may be substituted or unsubstituted.

As the heterocyclic group, nitrogen, oxygen, sulfur,
A 3- to 15-membered ring having at least one atom selected from selenium and tellurium is exemplified. More preferably, it is a 5- to 6-membered ring having at least one nitrogen atom. Examples of heterocyclic groups include pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole Or a group derived from a thiadiazole ring or the like.

Any _{two of} R ₁ , R ₂ and R ₃ may together form a 5- or 6-membered ring or multiple rings. These rings may be unsubstituted or substituted. The 5- or 6-membered ring or multiple rings formed by R ₁ , R ₂ and R ₃ may be alicyclic, or they may be the aromatic and heterocyclic groups described above.

[0029] R ₄ is a carboxylate, for example, acetate, formate, benzoate or trifluoroacetate, or other more or a salt of an acid of long chain or R _4,, 0 ^- a. w is 0 or 1. When R ₃ is a sulfo or carboxyl group, R ₄ represents 0 ⁻ and w is 0.

X^-Is suitable for use in photographic elements,
In addition, any compound that does not interfere with the fog suppression effect of the compound
It is an anionic counterion. Preferably, these pairs
ON is water-soluble. X^-A suitable example of_ThreeC
O_Two ^-, Cl^-, CF_ThreeSO_Three ^-, PF ₆ ^-, Br^-, BF_Four ^-,
AsF₆ ^-, CH_ThreeSO_Three ^-, CF_ThreeCO_Two ^-, CH_ThreeC₆H_FourS
O_Three ^-, HSO_Four ^-, SbF₆ ^-And CCl_ThreeCO_Two ^-Etc.
I can do it. Particularly useful is CH_ThreeCO_Two ^-, CH_ThreeSO
_Three ^-And PF₆ ^-It is.

Examples of the substituent for R ₁ , R ₂ and R ₃ and R ₄ include an alkyl group (for example, a methyl group, an ethyl group, a hexyl group, etc.) and an alkoxy group (for example, a methoxy group, an ethoxy group, Octyloxy group and the like), aryl group (for example, phenyl, naphthyl, tolyl), hydroxy group, halogen atom, aryloxy group (for example, phenoxy group and the like), alkylthio group (for example, methylthio group,
Butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), acyl group (eg, acetyl group, propionyl group, butyryl group, valeryl group, etc.), sulfonyl group (eg, methylsulfonyl group, phenylsulfonyl group, etc.), acylamino Group, sulfonylamino group, acyloxy group (for example, acetoxy group, benzooxy group, etc.),
Examples thereof include a carboxyl group, a cyano group, a sulfo group, and an amino group. Preferred substituents are lower alkyl groups (for example, those having 1 to 4 carbon atoms such as methyl group and ethyl group) and halogens (for example, chlorine and the like).

Specific examples of the aryliodonium compound represented by the general formula (2) of the present invention are shown below, but the present invention is not limited thereto.

[0033]

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Compounds 2-1, 2-2, 2-5, 2-1
0, 2-12, 2-16, 2-19, 2-24, 2-2
5 and 2-29 are examples of particularly preferred compounds for use in the present invention. The aryl iodonium compound represented by the general formula (2) of the present invention has an O
rg. Syn. 1961 and "Advanced O
rganic Chemistry "Fieser
& Fieser, Reinhold NY 1961
It can be easily synthesized by the reaction of an iodosoaryl compound with the corresponding anhydride, as described in the year.

[0035]

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Many of these compounds are commercially available.
In the present specification and claims, a group or a ring containing a substitutable hydrogen (for example, an alkyl group, an amino group, an aryl group, an alkoxy group, a heterocyclic ring, etc.) is unsubstituted or has a certain substituent. Unless otherwise specified as being only substituted, the term includes not only unsubstituted substituents but also those substituted with substituents which do not impair the advantages of the present invention. Suitable non-limiting substituents include those described for the substituents for R ₁ , R ₂ , R ₃ and R ₄ .

The amount of the aryl iodonium compound represented by the general formula (2) is about 1 × 10 ^-9 to 10 × 10 ^-3.
mol / mol Ag is preferable, and 10 × 10 ⁻³ mol / g is preferable.
molAg is a more preferred upper limit. The amount added depends somewhat on the point of addition. If the compound is added after precipitation, the preferred level is about 10 × 10 ^-7 to 1 × 10
^-3 mol / mol Ag. When the aryliodonium compound is added at the beginning of or during precipitation, the preferred range is from about 1 × 10 ^-9 to 1 × 10 ^-4 mol / m.
olAg.

The aryl iodonium compound represented by the general formula (2) can be added to a photographic emulsion using any appropriate technique. It may be dissolved in a common organic solvent such as methanol or acetone and added to the emulsion. It can also be added to the emulsion in a liquid / liquid dispersion similar to the technique used for certain couplers. These can be added as a solid particle dispersion. The aryl iodonium compound represented by the general formula (2) may be used in addition to any conventional stabilizers or antifoggants commonly used in the art. More than one aryl iodonium compound may be used in combination.

The photographic emulsions of the present invention are prepared by precipitating silver halide crystals in a colloidal matrix, generally by conventional methods in the art. This colloid is a typical hydrophilic film former, for example,
Gelatin, alginic acid or derivatives thereof.

The crystals formed in the precipitation step are washed and then the emulsion temperature is raised, usually by adding 40 ° C. to 70 ° C., by adding spectral sensitizing dyes and chemical sensitizers, and then maintained for a certain period of time. By performing such a heating step, chemical sensitization and spectral sensitization are performed. Precipitation and spectral and chemical sensitization used in preparing the emulsion used in the present invention may be any of the methods known in the art.

For the chemical sensitization of emulsions, usually sensitizers such as sulfur-containing compounds such as allyl isothiocyanate, sodium thiosulfate and allyl thiourea; reducing agents such as polyamines and stannous salts; For example, gold, platinum; and a polymer agent such as a polyalkylene oxide is used. As aforementioned,
Heat treatment is used to complete chemical sensitization. Spectral sensitization is performed with a combination of dyes that results in the desired wavelength range within the visible or infrared spectrum. Such dyes are known to be added both before and after the heat treatment.

Next, the disulfide compound used in the present invention will be described. The disulfide compound used in the present invention may have any structure.
Those represented by -SS-Ar are preferred. Where Ar
Is a heteroaromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms, or an aromatic or fused aromatic ring.

The disulfide compound used in the present invention includes a disulfide compound of the following mercapto compound or a disulfide compound of an aromatic mercapto compound. Examples of the mercapto compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole,
-Mercaptobenzothiazole, 2-mercapto-5-
Methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobisbenzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol,
2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8
-Mercaptopurine, 2-mercapto-4- (3H) quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy- 2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5
Mercapto-1,2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine,
2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole and the like can be mentioned. As the aromatic mercapto compound,
The aromatic ring, for example, a benzene ring, a naphthalene ring and the like preferably have a substituent, and as the substituent, for example,
Examples include a halogen atom, a hydroxy group, an amino group, a carboxy group, an alkyl group, an alkoxy group, a carboxamide group, a sulfamoyl group, and a sulfamide group. Specifically, 4,4'-dinonyldiphenyl disulfide,
4,4'-dioctyl sulfamide diphenyl disulfide and the like.

In the invention of claim 3 of the present invention, the glass transition point Tg of the matting agent is from 40 ° C. to 90 ° C., more preferably from 50 ° C. to 80 ° C., and a polymer matting agent is preferably used. The Tg of the polymer matting agent used is, for example, “J. Brandrup, EH.
Immergut, E .; A. Gulke co-authored POL
YMER HANDBOOK, 4th Edition
n, VI193 to VI253 (1999) ". In the case of a copolymer, it can be determined by the following formula.

1 / Tg = a1 / Tg1 + a2 / Tg2 +
... + an / Tgn Here, Tgn represents Tg of a homopolymer of monomer n, an is a polymerization fraction of monomer n in the polymer,
a1 + a2 +... + an = 1.

Specific examples of the composition of the polymer matting agent and its glass transition temperature (Tg) are shown below.

Matting agent composition Tg p-1) Poly (2-tert-butylphenylacrylate) 72 ° C. p-2) Poly (2-chlorophenylate) 53 ° C. p-3) Poly (4-methoxyphenylacrylate) 51 ° C. p-4 Poly (phenylacrylate) 57 ° C p-5) Poly (acrylamide) 165 ° C p-6) Poly (N-butylacrylamide) 46 ° C p-7) Poly (N, N-dibutylylamide) 60 ° C 60 ° C 0 ° C p-9) Poly (benzylmethylacrylate) 50 ° C p-10) Poly (sec-butylmethacrylate) a) 60 ° C. p-11) Poly (cyclobutylmethacrylate) 78 ° C. p-12) Poly (cyclomethylmethacrylate) 42 ° C. p-13) Poly (methylmethacrylate) 105 ° C. poly (methyl) poly (110) Crypt. (ethyleneacrylate) 27 ° C p-16) Poly (ethylene-co-methacrylic acid) ionomer 57 ° C p-17) Poly (vinylchloride-co-vinylate state) 69 ° C In the invention of claim 4 of the present invention, the hydrophilic colloid is a layer according to claim 4 of the present invention. The total film thickness is less than 3.5 μm, and 0.8 μm or more.
It is preferably less than 5 μm, more preferably 1.2 to 3.0 μm. The thickness is preferably less than 3.5 μm from the viewpoint of ultra-rapid processing (45-second dry-to-dry) of a photosensitive material for ultra-rapid provision of emergency medical image information. Further, it is preferable that the film thickness is not too thin in order to prevent undesired scratches and the occurrence of roller marks.
m or more, and more preferably 1.2 μm.

The average particle size of the matting agent is 1.1 to 2.0 times the total thickness of the hydrophilic colloid layer, preferably 1.1 to 1.9 times, more preferably 1.2 to 1.8 times. More preferred. The matting agent is preferably a monodisperse matting agent. The relative standard deviation of the matting agent particle diameter is preferably 30% or less, more preferably 20% or less.

The proportion of the number of matting agents whose center of gravity of the matting agent is located in the hydrophilic colloid layer is 50% or more and 100% or less, preferably 70% or more and 100% or less, more preferably 85% or more of the matting agent. 100% or less is more preferable. It is at least 50% from the viewpoint of preventing the matting agent from spalling and easily causing conveyance failure, and the higher this ratio is, the more the matting agent is spalled, which is preferable. This is because, in addition to the matting agent particle diameter and the total thickness of the hydrophilic colloid layer being within the range of the present invention, "when the matting agent is added to the emulsion layer" or "when the matting agent is added to the protective layer, By simultaneously coating the emulsion layer and the protective layer (the matting agent hardly sinks into the emulsion layer if the emulsion layer is coated and dried and then the protective layer is coated).

The “ratio of the number of matting agents whose center of gravity of the matting agent is located in the hydrophilic colloid layer” is defined as “a matting agent observed on the cross section by taking an electron micrograph of a cross section of the film. Is N1, and the number of matting agents whose center of gravity is inside the film surface is N2. N1 is at least 200 or more, and (N1 / N2) × 100 = “the ratio of the number of matting agents whose center of gravity of the matting agent is located in the hydrophilic colloid layer”.

The silver halide emulsion used in the present invention may have any halogen composition, for example, any of silver chloride, silver iodochloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide. May be used.

When silver iodide is contained, the silver iodide content is from 0 to 1.0 as an average silver iodide content of the whole silver halide grains.
5 mol% is preferable, and 0 to 1.0 mol% is more preferable.

The average grain size of the silver halide grains is 0.15 to
5.0 μm, preferably 0.2 to 4.0 μm
Is more preferable, and most preferably 0.3 to 3.0 μm. The average particle diameter of the silver halide grains is a diameter in terms of sphere.

The crystal habit of the silver halide grains may be of any crystal habit such as cubic, octahedral, and twin plane, but is preferably tabular silver halide grains (hereinafter simply tabular grains). ). A tabular silver halide grain refers to a grain having two opposing parallel main planes, and the one used in the present invention has a (111) plane as a main plane or a (100) plane as a main plane. Or both.

The tabular silver halide grains preferably used in the present invention have an average value of the ratio of the grain size to the grain thickness (hereinafter referred to as aspect ratio) of 2 or more, and preferably 3 to 70. Particularly preferably, it is 3 to 40, most preferably 4 to 15.

Here, the grain size is an average projected area diameter, and is represented by a circle equivalent diameter of a projected area of a tabular silver halide grain (diameter of a circle having the same projected area as the silver halide grain). And thickness indicate the distance between two parallel main planes forming tabular silver halide grains.

When tabular grains are used in the present invention, the average thickness of the grains is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.60 μm, and even more preferably 0.05 to 1.0 μm. 0.50 μm. The average particle size is 0.
It is preferably from 15 to 5.0 μm, and from 0.4 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
4 to 2.0 μm. The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grains / average grain size) × 100 = width (%) of grain size distribution When it is defined, it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

Tabular silver halide grains can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodide ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution.

The tabular silver halide grains are formed by a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt) and an iron It is preferable to add a metal ion using at least one selected from salts (including complex salts) and to include these metal elements inside the particles and / or on the surface of the particles.

The process for producing a silver halide emulsion used in the light-sensitive material of the present invention is roughly classified into a grain forming process, a desalting process, a chemical sensitizing process and the like. 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.

Applying the reduction sensitization during the production process of the silver halide emulsion basically means that any of the above-mentioned processes may be used. Reduction sensitization may be performed at the initial stage of grain formation, such as nucleation, physical ripening, or growth, or may be performed prior to chemical sensitization other than reduction 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 reducing sensitization after desalting. Here, "growing" means that reduction sensitization is performed while 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 sensitizing and then growing further.

Reduction sensitization refers to a method in which a reducing agent is added to a silver halide emulsion, or a low pAg of 1 to 7, which is called silver ripening.
A method of growing or ripening in an Ag atmosphere,
Either growing in an atmosphere of high pH of 8 to 11 called high pH ripening or ripening method can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted. Examples of the reduction sensitizer include stannous salts, amine and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like. In the present invention, these compounds can be selected for use, and two or more of these compounds can be used in combination. Stannous chloride, thiourea dioxide, and dimethylamine borane are preferred compounds as the reduction sensitizer. The addition amount of the reduction sensitizer depends on the production conditions of the emulsion, so it is necessary to select the addition amount.
The range of ^-7 to 10 ^-3 mol is suitable.

In the light-sensitive material of the present invention, an ascorbic acid derivative can be used as a reduction sensitizer. These ascorbic acid compounds are desirably used in a larger amount than the amount of the conventional reduction sensitizer which is preferably used. For example, Japanese Patent Publication No. 57-33572 states that the amount of a reducing agent is usually 0.75 × 10 ^-2 meq.
× 10 ^-4 mol / AgX mol). 0.1 to 10 mg per kg of silver nitrate (10 ascorbic acid
^-7 to 10 ^-5 mol / AgX mol) is effective in many cases. " The ascorbic acid compound is used for the emulsion grain size, silver halide composition, emulsion preparation temperature, pH,
The preferred amount of addition depends on factors such as pAg.
It is preferable to select a range of 5 × 10 ^-5 to 1 × 10 ^-1 mol per mol of silver halide, more preferably 5 × 10 ^-5 mol.
It is preferable to select a range of ^-4 to 1 × 10 ^-2 mol. It is particularly preferable to select from the range of 1 × 10 ⁻³ to 1 × 10 ⁻² mol. The ascorbic acid compound 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. Particularly preferred is a method of adding during grain growth. It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle formation is preferable. Alternatively, a reduction sensitizer 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 solution of the reduction sensitizer in several portions as the grains are formed or to continuously add the solution for a long time.

In the method for chemically sensitizing silver halide grains of the present invention, gold sensitization, sulfur sensitization, sensitization with a chalcogen compound, and a combination thereof are preferably used. As the chemical sensitization method, so-called sulfur sensitization, gold sensitization, sensitization with a noble metal of Group VIII of the peri-disciplinary table (for example, Pd, Pt, etc.), and a sensitization method using a combination thereof can be used. Among them, a combination of gold sensitization and sulfur sensitization, or a combination of gold sensitization and sensitization with a selenium compound is preferable. The addition amount of the selenium compound can be arbitrarily set, but it is preferable to use it together with sodium thiosulfate during chemical sensitization. More preferably, the molar ratio of the selenium compound to sodium thiosulfate is 2: 1 or less. More preferably, it is used in a molar ratio of 1: 1 or less. It is also preferable to carry out the reaction in combination with the reduction sensitization.

In the case of selenium sensitization, a conventionally known selenium sensitizer can be used.
Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). urea,
N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4- Nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone,
Selenoacetophenone, etc.), selenoamides (for example,
Selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), and selenophosphates (eg,
Tri-p-triselenophosphate, etc.) and selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones. The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. Depending on the properties of the selenium compound to be used, the addition method may be a method in which water or an organic solvent such as methanol or ethanol is dissolved alone or in a mixed solvent, or
A method in which the mixture is added in advance with a gelatin solution or a method disclosed in JP-A-4-140739, that is, a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used. The temperature for chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90 ° C. More preferably, it is 45 to 80 ° C. Moreover, pH is 4-9, pA
g is preferably in the range of 6 to 9.5.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of the chemical sensitization in terms of sensitivity and adsorption of photosensitive dye. In particular, a method of adding silver iodide in the form of fine grains is preferable.

The chemical sensitization is preferably carried out in the presence of a compound having adsorptivity to silver halide.
Among azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, and azaindenes, particularly preferred are compounds having a mercapto group and compounds having a benzene ring.

Further, US Pat. No. 3,615,613,
The combinations described in JP-A Nos. 3,615,641, 3,617,295, and 3,635,721 are particularly useful.

The silver halide grains of the present invention are spectrally sensitized using a spectral sensitizing dye (hereinafter, simply referred to as a sensitizing dye). Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. The sensitizing dye is used in the same concentration as that used for a normal negative-working silver halide emulsion. In particular, it is advantageous to use the silver halide emulsion at a dye concentration that does not substantially lower the intrinsic sensitivity of the silver halide emulsion. Sensitizing dye 1.0 × 10 ⁻⁵ mol to 5 mol per mol of silver halide
× preferably used 10 ^-4 mol, is preferably used, especially of silver halide per mole of sensitizing dye at 4 × 10 ^-5 mol to 2 × 10 ^-4 molar.

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like. A renin nucleus, a benzindolenine nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye includes pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thioparbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. Further, together with the sensitizing dye, the dye itself does not have spectral sensitization or a substance that does not substantially absorb visible light, and has a supersensitizing effect, such as a nitrogen-containing heterocyclic nucleus group. It may contain a substituted aminostilbene compound, an aromatic organic formaldehyde condensate, a cadmium salt, an azaindene compound and the like.

The sensitizing dye is preferably added as a solid fine particle dispersion, rather than dissolved in an organic solvent. Particularly, the sensitizing dye is dispersed in an aqueous system free of an organic solvent and / or a surfactant. It is preferably added in the form of a solid fine particle dispersion which is hardly soluble in water. Particle size after dispersion is 1 μm
The following is preferred.

The hydrophilic roller used in the light-sensitive material of the present invention
It is preferable to use gelatin as the
However, other hydrophilic colloids can also be used.
You. For example, gelatin derivatives, gelatin and other macromolecules
Proteins such as graft polymers, albumin, casein, etc.
Hydroxyethyl cellulose, carboxymethyl cell
Cellulose such as loin and cellulose sulfates
Derivatives, sodium alginate, dextran, starch derived
Body, polyvinyl alcohol, polyvinyl alcohol part
Min acetal, poly-N-vinylpyrrolidone, polyac
Lylic acid, polymethacrylic acid, polyacrylamide, poly
Vinylimidazole, polyvinylpyrazole, etc.
Uses various kinds of synthetic hydrophilic polymer materials such as copolymers
be able to. In particular, the average molecular weight is 5, together with gelatin.
000 to 100,000 dextrin and polyacrylamide
It is preferable to use them in combination. Lime-treated gelatin for gelatin
, Acid-treated gelatin, Bull. Soc. Photo. ,
Japan, No. 16, 30 (1966)
Enzyme-treated gelatin as well as gelatin derivatives
(For gelatin, for example, acid halides, acid anhydrides, isocyanates
Salts, bromoacetic acid, alkane sultones, vinyl sulfite
Honamides, maleamide compounds, polyalkylene
Antioxidants, epoxy compounds, etc.
Correspondingly obtained). Preferred gelatin
4.0 g / m per side of photosensitive material ^TwoUsing
Preferably 3.0 g / m^TwoYou can use
More preferred, most preferably 2.5 g / m^TwoIt is.

When any one of the silver halide emulsion layers or the constituent layers other than the emulsion layers of the light-sensitive material of the present invention contains a dye capable of decoloring or flowing out during development, high sensitivity and high sensitivity can be obtained.
A photosensitive material having high sharpness and suitability for rapid processing can be obtained. The dye used in the photosensitive material can be appropriately selected from dyes capable of improving sharpness by absorbing a desired wavelength and removing the influence of the wavelength according to the photosensitive material. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the color is not visible when the image is completed.

The dye is preferably added as a solid fine particle dispersion. The method for producing the solid fine particle dispersion includes, specifically, a ball mill, a vibration mill, a planetary mill, and a surfactant. It can be prepared using a fine dispersing machine such as a sand mill, a roller mill, a jet mill, and a disk impeller.

Further, a method of dissolving a dye in a weak alkaline aqueous solution and lowering the pH to make it weakly acidic to precipitate fine particulate solids, or simultaneously adjusting the pH of a weakly alkaline solution of the dye and the acidic aqueous solution while adjusting the pH. A dye dispersion can be obtained by a method of preparing a particulate solid by mixing.

The dyes may be used alone, or two or more dyes may be used in combination. When two or more dyes are used in combination, they may be dispersed individually and then mixed.
Also, they can be dispersed at the same time.

The constituent layer of the light-sensitive material to which the dye is added and contained is preferably a silver halide emulsion or a layer closer to the support or both, and more preferably a coating layer adjacent to the transparent support. It is effective to add.
It is desirable that the concentration of the dye is higher on the side closer to the support.

The amount of the dye to be added can be changed according to the target of sharpness. Preferably 0.2 to 20 mg /
m ² , more preferably 0.8 to 15 mg / m ² .

In the light-sensitive material of the present invention, the silver halide emulsion layer is preferably colored. In this case, a dye is added to the silver halide emulsion before coating or to an aqueous solution of a hydrophilic colloid to support these liquids. It may be applied to the body by various methods directly or via another hydrophilic colloid layer.

As described above, it is preferable that the concentration of the dye is higher on the side closer to the support, but in order to fix such dye on the side closer to the support, it is necessary to use a mordanting agent. it can. For example, a non-diffusible mordant can be used to bind to at least one of the aforementioned dyes.

The method for combining the dye with the non-diffusible mordant is carried out by various methods known in the art.
In particular, a method of binding in a gelatin binder is preferably applied. In addition, a method for binding in an appropriate binder and dispersing in an aqueous gelatin solution by ultrasonic waves or the like can be applied. Although the binding ratio varies depending on the compound, usually, 0.1 part to 10 parts of the nondiffusible mordant is bound to 1 part of the water-soluble dye. Since the amount added as the water-soluble dye is linked to the non-diffusible mordant, it is preferable to use the dye alone.

When incorporated in the light-sensitive material, a constituent layer having a combination of a dye and a non-diffusible mordant may be newly provided as a constituent layer, and its position can be arbitrarily selected.
Preferably, it is effective to use as a coating layer adjacent to the transparent support.

As the surfactant for preparing the solid particulate dispersion, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used. For example, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines and the like Preferred are anionic surfactants and nonionic surfactants such as saponins, alkylene oxide derivatives, alkyl esters of sugars and the like.

The amount of the anionic surfactant and / or the nonionic surfactant is not uniform depending on the kind of the surfactant or the dispersing condition of the dye, but is usually 0.1 to 2000 mg / g of the dye. And preferably 0.5 to 1000 mg, more preferably 1 to 500 mg.

The concentration of the dispersion of the dye is from 0.01 to
10 mass% is preferable, and 0.1 to 5 mass% is more preferably used. It is preferable to add the surfactant before the start of the dispersion of the dye, and it is preferable to further add the dye dispersion after the completion of the dispersion, if necessary. Each of these anionic surfactants and nonionic surfactants may be used alone, and it is also preferable to use both surfactants in combination.

The emulsion may be subjected to a Nudel washing method, a flocculation sedimentation method, or the like to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication No. 35-160.
No. 86, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group, or a desalination method using a polymer flocculant, eg, G-3, G-8, etc. described in JP-B-63-158644. Can be.

Various photographic additives can be used in the light-sensitive material of the present invention. Examples of known additives include Research Disclosure (RD) 17643.
(December 1978), 18716 (1979) and 308119 (December 1989). These places are listed below.

[0091]

[Table 1]

When the emulsion used in the light-sensitive material of the present invention is coated on only one side of the support, the layer containing the antihalation dye is usually placed between the emulsion and the support, even if the support is sandwiched. Although it may be on the opposite side of the layer, it is preferable to provide it as the back layer on the opposite side of the emulsion layer because the range of choice of dyes is widened. The transmission density of the dye content at the wavelength of the exposure light source is preferably 0.4 to 1.5, more preferably 0.45 to 1.5.
-1.2 is more preferable.

The method of adding the dye includes, for example, the addition of an aqueous solution, the addition of a micelle, and the addition of a solid, depending on the nature of the dye.

As the support preferably used in the light-sensitive material of the present invention, those described in the above RD can be mentioned. Suitable supports include polyethylene terephthalate film, polyethylene naphthalate (PEN) and the like. An undercoat layer may be provided on the surface to improve the adhesiveness of the coating layer, and may be subjected to corona discharge, ultraviolet irradiation, or the like.

Next, the developer used in the present invention will be described. The compound used as a developing agent may contain the following developing agents for black and white development. For example, reductones (ascorbic acid, erythorbic acid); dihydroxybenzenes (hydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, potassium hydroquinone disulfonate, sodium hydroquinone disulfonate, etc.); and 3-pyrazolidones (1 -Phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl- 3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2 -Benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone and the like; as aminophenols (o-aminophenol, p-aminophenol, N-
1-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.);
(1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p
-Methylaminophenyl) -3-aminopyrazoline, 1
-(P-amino-m-methylphenyl) -3-aminopyrazoline and the like; pyrazolones (4-aminopyrazolone and the like) or a mixture thereof. Of the pyrazolidones, particularly, dimesone and dimesone S substituted at the 4-position are particularly preferable since they have little change over time in the water-soluble or solid processing agent itself.

The developer (liquid) may further contain a preservative (sulfite, bisulfite, etc.) and a buffer (carbonate,
Borates, borates, sugars, phosphoric acid, etc.), alkaline agents (sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, etc.), dissolution aids (polyethylene glycols, esters thereof, etc.) Contains pH adjusters (organic acids such as citric acid and tartaric acid), sensitizers (quaternary ammonium salts, etc.), development accelerators, hardeners (dialdehydes such as glutaraldehyde), surfactants, etc. Can be done. Further, as an antifoggant, an azole organic antifoggant (indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole, thiadiazole)
Alternatively, a masking agent (sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, etc.) for masking calcium ions mixed in tap water may be added.
Further, as a silver stain preventing agent, for example, JP-A-56-2434
7, JP-B-56-46585, JP-B-62-284
No. 9, JP-A-4-362942 and the like can be used. In addition, L. F. A. Mason, Photographic Processing Chemistry, Focal Press (1966) 22-22
9, U.S. Pat. Nos. 2,193,015 and 2,592,
No. 364 and JP-A-48-64933 may be used.

PH at the time of use of the developer used in the present invention
Is preferably in the range of 9 to 12, more preferably 9.5 to
10.5.

The developing solution, fixing solution and stabilizing solution used in the present invention are preferably provided to the user in the form of a concentrated solution or solid. To solidify the processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. (See, for example, JP-A-4-29136, JP-A-4-85535, JP-A-4-85536, and JP-A-4-855.)
No. 33, No. 4-85534, No. 4-172341, and the like. In the present invention, when a developer or a fixer is supplied as a tablet, the binder is disclosed in JP-A-7-295161 (23).
To pp. 30) (monosaccharides, polysaccharides in which a plurality of monosaccharides are linked to each other, and their decomposed products), and dextrins and sugar alcohols are particularly preferably used. There is little change in shape during long-term storage, and trouble during addition and usability are improved.

[0099] The solid processing agent includes a lubricant as disclosed in
It is preferable to use acylated amino acids described in JP-A-92624 (pages 9 to 15). By this method, a solid processing agent can be stably produced without impairing the strength, the solubility is less deteriorated, and the storage stability and dust generation are improved. Organic sulfur compounds are also preferred.

The solid processing agents include coating agents such as hydroxylamines, phenylcarboxylic acids,
It is preferable to use phenylsulfonic acids, alkyl (or alkenyl) carboxylic acids into which a hydroxyl group or a carboxyl group has been introduced, sulfites, water-soluble polymers (polyalkylene glycol, methacrylic acid type betaine-type polymer, etc.), and saccharides. The generation of fine powder is small, the deterioration of solubility is small, and excellent storability can be maintained and stable photographic performance can be maintained.

The development temperature is preferably 25 to 50 ° C.
And more preferably 30 to 40 ° C. The development time is preferably from 3 to 20 seconds, more preferably from 5 to 15 seconds. The total processing time is preferably Dry to Dry
15 to 45 seconds.

The replenishment of the developer replenishes the processing agent fatigue and the oxidation fatigue equivalent. As a replenishment method, Japanese Patent Application Laid-Open No. 55-126
No. 243, replenishment by feeding speed,
Japanese Patent Application Laid-Open No. 1-14991
Area replenishment controlled by the number of sheets continuously processed described in No. 56 may be used, and the replenishment amount is preferably 200 ml / m ² or less per m ² of the photographic material, and more preferably 8
It is a 0~150ml / m ^2.

[0103]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of Seed Emulsion-1> A1 Ossein gelatin 24.2 g Distilled water 9657 ml Polypropyleneoxy-polyethyleneoxy-disuccinate-sodium salt (10% methanol solution) 6.78 ml KBr 10.8 g 10% AgNO ₃ aqueous solution 114 ml B1 2.5N AgNO ₃ aqueous solution 2825 ml C1 KBr 841 g Finish to 2825 ml with water D1 1.75 N KBr aqueous solution The following silver potential control amount 442 each of solution A1 and solution B1 and solution C1 using a mixing stirrer at 42 ° C. .3 ml were added by the double-mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature was raised to 50 ° C. over a period of 40 minutes by heating to 3% K
After adjusting the pH to 5.0 with an aqueous OH solution, the solution B was again used.
1 and the solution C1 were each 55.4 m
Added at a flow rate of 1 / min for 42 minutes. 42 ℃ to 50
The silver potential (measured with a silver ion-selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during heating up to 0 ° C. and addition of the solution B1 and the solution C1 by the re-mixing method was +8 mV using the solution D1. And +16 mV.

After the addition, the pH was adjusted to 6 with a 3% aqueous KOH solution.
After adjusting to, immediate desalting and washing were performed. Seed emulsion-1 thus obtained is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 for 90% or more of the total projected area of silver halide grains. The average thickness is 0.045 μm, and the average particle size (circular diameter conversion) is 0.42 μm.
m was confirmed by an electron microscope. The variation coefficient of the thickness was 42% and the variation coefficient of the distance between twins was 45%.

<Preparation of Tabular Silver Bromide Emulsion-1> Seed Emulsion
A tabular silver bromide emulsion was prepared using the following three solutions.

A2 Ossein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate-sodium salt (10% methanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3669 ml with water B2 KBr 1747 g To 3669 ml with water Finishing C2 AgNO ₃ 2493 g Finishing to 4193 ml with water The solution A2 was vigorously stirred in a reaction vessel while maintaining the temperature at 50 ° C., and the total amount of the solution B2 and the solution C2 was added thereto over 100 minutes by a double jet method. During this time, the pH was kept at 9.0 with a 3% KOH aqueous solution, and the pAg was kept at 8.6 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed functionally with time so as to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and so that they did not become multi-components due to Ostwald ripening.

After completion of the addition, the emulsion was cooled to 40 ° C.
As an aggregating polymer agent, 1800 ml of an aqueous solution of 13.8% (by mass) of modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added and stirred for 3 minutes. afterwards,
An aqueous solution of acetic acid 56% (mass) was added to adjust the pH of the emulsion to 4.6, stirred for 3 minutes, allowed to stand for 20 minutes, drained the supernatant by decantation, and further added 11.25 L of distilled water. After the addition and stirring, the supernatant was drained.

Subsequently, an aqueous gelatin solution and a 10% (by mass) aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average thickness was 0.16 μm, the average particle diameter (in terms of circular diameter) was 0.84 μm, and the ratio to the average aspect was about 5.3. This was a tabular silver bromide emulsion containing tabular silver halide grains having a size distribution of 20%. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide.
Met.

After the emulsion prepared above was heated to 55 ° C., the following spectral sensitizing dye (A) 45 was added per mole of silver halide.
0 mg and 45 mg of spectral sensitizing dye (B) were added.
100 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) were added. Part 10
Minutes later, 3.5 mg of chloroauric acid, 10% of sodium thiosulfate
mg and 100 mg of ammonium thiocyanate were added. After a further 40 minutes, the following silver iodide fine grains (* 1) were added to 0.
3 mol, 10 minutes later 5 mg of triphenylphosphine selenide was added and 40 minutes later (TAI)
Five minutes after the addition of 500 mg, 13 g of trimethylolpropane and 30 g of gelatin were added, and the mixture was rapidly cooled to gel the emulsion, thereby completing the chemical sensitization. This emulsion was designated as tabular silver bromide emulsion-1.

Sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine-sodium salt anhydride Sensitizing dye (B): 5 5,5'-Di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride (* 1) Preparation of silver iodide fine particles A3 Océ in-gelatin 100 g KI 8.5 g distilled water to 605ml with B3 AgNO ₃ 360 g of distilled water to 2000ml with C3 KI 352 g solution A3 in the reaction vessel to 605ml with distilled water was added, with stirring maintained at 40 ° C., The solution B3 and the solution C3 were added thereto at a constant speed by a simultaneous mixing method over 30 minutes. The pAg during the addition was kept at 13.5 by a conventional pAg control means. The formed silver iodide fine particles are α-AgI and β-Ag having an average particle size of 0.06 μm.
I was a mixture.

The following additives were added to the tabular silver bromide emulsion-1 obtained above to prepare an emulsion layer coating solution, and at the same time, a protective layer coating solution. The matting agents shown in Table 2 were added as shown in Table 2.

The amount of silver applied per side was 1.7 g / m 2
Amount with gelatin ² performs double-sided simultaneous coating the emulsion layer is 1.8 g / m ^2, the protective layer on the support using two slide hopper type coater so that 0.6 g / m ^2, dried A sample was obtained. The support had a thickness of 175 μm and a concentration of 0.1 μm.
On both sides of a polyethylene terephthalate film base for X-ray colored blue at 15, the concentration of a copolymer composed of three monomers of 50% by mass of glycidyl methacrylate, 10% by mass of methyl acrylate, and 40% by mass of butyl methacrylate was increased to 10% by mass. The following filter dye and gelatin were dispersed in an aqueous copolymer dispersion obtained by diluting as described below and applied as an undercoat liquid.

[0116]

Embedded image

The additives added to the tabular silver bromide emulsion-1 are as follows. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene maleic anhydride copolymer 2.5 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g Antifoggant (described in Table 2) Amount described in Table 2

[0119]

Embedded image

Protective Layer Coating Solution The following was prepared as a protective layer coating solution. The additive is coating liquid 1.
Shown in the amount per 1.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2.0 g Sodium-i-amyl-n-decylsulfosuccinate 0.1 g (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ (hardener) 500 mg C ₄ F ₉ SO ₃ K 2.0 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0122]

Embedded image

The obtained sample was processed in a developing machine obtained by modifying a roller transport type automatic developing machine SRX-502 (manufactured by Konica Corporation) using a developing solution and a fixing solution having the following composition under the following conditions. The results are shown in Table 2.

(Developer composition) Part A (for finishing 12 L) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 140 mg 1-phenyl -5-Mercaptotetrazole 250 mg 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 102 g Hydroquinone 390 g Diethylene glycol 550 g Add water to make up to 6000 ml Part B (for finishing 12 liters) Glacial acetic acid 70 g 5-Nitroindazole 0. 6 g glutaraldehyde (50% solution) 8.0 g n-acetyl-D, L-penicillamine 1.2 g (starter) glacial acetic acid 120 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (C H ₂ ) ₂ OH 1 g KBr 225 g CH ₃ N (C ₃ H ₆ NHCONHCH ₂ SC ₂ H ₅ ) ₂ 1 g Add water to finish to 1 liter (fixing solution composition) Part A (18.3 liter finishing) Ammonium thiosulfate (70 Weight / vol%) 4500 g Sodium sulfite anhydride 450 g Sodium acetate trihydrate 450 g Tartaric acid 100 g Sodium citrate 10 g Gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Glacial acetic acid 330 g Aluminum sulfate 62 g Finish up to 7200 ml with pure water To prepare a developer, add parts A and B simultaneously to about 5 l of water, add water while stirring and dissolving to make up to 12 l, and adjust the pH to 10.53. This is used as a development replenisher.

To 1 liter of this replenisher, 20 ml of the above-mentioned starter was added to adjust the pH to 10.30, and the solution was used. The fixing solution is prepared by adding Part A to about 5 l of water, adding water while stirring and dissolving to make up to 18.3 l, adjusting the pH to 4.6 with sulfuric acid and ammonia, and using this as a replenisher for fixing solution. The replenishing amount of the developing solution, and the photosensitive material 1 m ² per 170ml in the fixing solution both.

The temperature of the developing solution is 35 ° C. and the temperature of the fixing solution is 33 ° C.
The time required for all processing steps was 45 seconds.

<Evaluation of Scratch Resistance> The unexposed sample film was allowed to stand at 23 ° C. and a relative humidity of 40% for 2 hours, and then 100 g using a commercially available nylon scrub under the same conditions.
After rubbing with a load of / cm ² , processing was performed with an automatic developing machine under the above conditions, and the evaluation was made by visual observation.

A: Almost no scratches B: Not practically problematic, but slightly scratched C: Scratching is noticeable and practically problematic D: Extremely large scratching, scratch width <Evaluation of Kutzuki resistance> The same sample conditioned for 12 hours under the air-conditioning conditions of 23 ° C. and 80% RH was superposed, and 20 g /
The weight is applied so that the pressure of cm ² is applied and left for 3 days.
The degree of stickiness between the films was evaluated in four steps as follows. A level higher than the BC level (intermediate level between B and C) has no practical problem.

A: no dustiness B: dustiness area about 5% C: dustiness area about 10% D: dustiness area 15% or more <Evaluation of transportability> Ten sets were transported in 100 pieces of one cut size, and the number of occurrences of defective transport was measured.
Each time the type of sample was changed, the suction cup was cleaned with gauze moistened with alcohol. The sample is 23 ° C 20% RH, 23 ° C 8
Each was conditioned at 0% RH for 2 hours, and the transportability was evaluated under the same conditions.

[0130]

[Table 2]

As is clear from Table 2, Samples 3 to 9 of the present invention in which a matting agent was added to the emulsion layer and a fog inhibitor was added (the constitutions of the first and second aspects of the present invention), and Samples 10 to 16 of the present invention in which a matting agent having a glass transition point of 40 ° C. or more and 90 ° C. or less were added to the emulsion layer (the structure of the invention according to claim 3 of the present invention) have poor scratch resistance, dustiness, and transportability. It turns out that it is excellent.

Example 2 A sample was prepared and evaluated in the same manner as in Example 1 except that the amount of silver applied per side, the amount of gelatin, and the matting agent were as shown in Table 3 on one side. Table 3 shows the results.

[0133]

[Table 3]

As is clear from Table 3, it is understood that the samples 5, 7, 9, 11, and 12 of the present invention (the structure of the invention according to claim 4 of the present invention) have excellent resistance to dust and transportability. .

[0135]

According to the present invention, even in the case of long-term use of various automatic conveyance devices for silver halide photographic light-sensitive materials, conveyance deterioration occurs due to deterioration of the material of the conveyance suction cup and adhesion of the peeled matting agent to the suction cup. It is possible to provide a silver halide photographic light-sensitive material which is free from deterioration of scratch resistance.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of a support, wherein at least one of the emulsion layers contains a matting agent and a fog inhibitor. A silver halide photographic light-sensitive material characterized by containing: 2. The fog inhibitor is a mercapto compound represented by the following general formula (1), an aryl iodonium compound or a disulfide compound represented by the following general formula (2). 3. The silver halide photographic light-sensitive material described in 1. above. Embedded image [Wherein, Z represents = N- or = C (X)-(X represents an alkyl group or an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl having a hydrophilic group. Represents a group or an aryl group. [Chemical formula 2] [Wherein, R ₁ , R ₂ and R ₃ are each a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, a hydroxy group, a halogen atom, an aryloxy group, an alkylthio group, an arylthio group, an acyl Represents a group, a sulfonyl group, an acyloxy group, a carboxyl group, a cyano group, a nitro group, a sulfo group, an alkylsulfoxide group or a trifluoroalkyl group, and any _{two of} R ₁ , R ₂ and R ₃ together represent 5 or It may form a 6-membered ring or multiple rings. R ₄ represents a carboxylate or 0 ⁻ . X ⁻ represents an anionic counter ion, and w is 0 or 1. When R ₃ is a carboxyl group or a sulfo group, R ₄ represents 0 ⁻ and w is 0. ] 3. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of a support, wherein at least one of the emulsion layers contains a matting agent in the emulsion layer. And a glass transition point of the matting agent is 40 ° C. or more and 90 ° C. or less. 4. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a support and containing a matting agent, the hydrophilic side of which has the emulsion layer. 3.5μ total colloid layer thickness
m, the particle size of the matting agent is 1.1 to 2.0 times the total thickness of the hydrophilic colloid layer, and the center of gravity of the matting agent is in the hydrophilic colloid layer. A silver halide photographic light-sensitive material, characterized in that the ratio of the number of matting agents is 50% or more.