JPH04156448A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To improve high sensitivity and pressure resistance by forming silver halide grains contained in an emulsion layer of specific crystal faces, concentrating dislocation in the proximity of the tops of the grains, and adding oxidant to silver during the manufacturing process of silver halide emulsion. CONSTITUTION:Silver halide grains contained in an emulsion layer are mainly composed of (111) faces. Dislocation is concentrated in the proximity of the tops of the grains. During the manufacturing process of silver halide emulsion, oxidant to silver is added. 60% or more, preferably 80% or more of the surface area of the grain is composed of (111) faces. The grain is preferably formed in a flat plate. In the configuration of the grain, aspect ratio is 3 or more, preferably 3 to 8. Dislocation density in the proximity of the top is twice or more, preferably four times, and specially preferably ten times or more as high as that of other peripheral part or a central part of the grain. As the oxidant to silver, compound for transforming fine silver atoms produced as by products in a process to manufacture silver halide grains into silver ions is effectively employed. Thus, high sensitivity and pressure resistance can be improved.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide emulsion and a photographic photosensitive material using the same.
Regarding materials, silver halide grain milk with particularly excellent photographic sensitivity is used.
This invention relates to a photosensitive agent and a photographic material using the same.
. (Conventional technology) The basic performance required of silver halide photographic materials is high sensitivity.
The fog is low in degrees. Also, there are no handling problems.
At the same time, it is also desirable. Especially in recent years, the sensitivity of silver halide color light-sensitive materials has increased and
Smaller formats are becoming more and more sensitive and image quality is increasing.
Excellent color photographic materials are strongly desired. Regarding observation of dislocations in silver halide grains, ■ C, R,
Berry, J. pp1. Phys, 2ヱ, 6
36 (1956) ■ C, R, Berry, D, C, S
kilman, J, 8pp1. Phys., 35. ■J, F, Hamilton, Phot, Sci, En
g,, 11, 57 (1967) ■T, Shiozaw
a, J, Soc, Phot, Sci, Jap, , 34
．． 16 (1971) ■T, Shiozawa+J, So
c, Photo, Sci, J・4+':,,”:,:
There are literatures such as t'l')'/2), and X-ray diffraction method or
Observation of dislocations in crystals using low-temperature transmission electron microscopy
It is possible to and intentionally distort the crystal.
It has been mentioned that various dislocations occur in the crystal due to
It's being ignored. The silver halide grains in these documents were used during the formation of photographic emulsions.
It is possible that dislocations were introduced in the image.
JP-A-63-220 for silver halide grains with m
238, Unexamined Japanese Patent Publication No. 1999-1. It is described in -201649. child
According to these patents, tabular grains with a certain amount of dislocation lines introduced
Compared to tabular grains without dislocation lines, grains have higher sensitivity and reciprocity.
Which photographic properties are excellent and which are used in photosensitive materials?
It has been shown to have excellent sharpness and graininess, but currently
I can't be satisfied with that. (Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned prior art. First, the present invention uses a silver halide emulsion with high sensitivity.
The object of the present invention is to obtain a silver halide photographic light-sensitive material. Second, silver halide emulsions with excellent pressure resistance are used.
The object is to print a silver halide photographic light-sensitive material. (Means for Solving the Problems) The RIIF of the present invention is as follows: (1) At least one layer of halogenation on the support. silver emulsion layer
In the silver halide photographic light-sensitive material having the emulsion layer
The silver halide grains contained in
The dislocations are concentrated near the apex of the particle.
, an oxidizing agent for silver during the manufacturing process of the silver halide emulsion
A silver halide photographic material characterized by the addition of
! '81゜(2) The oxidizing agent for silver has the formula (+), (II
) or (III).
The silver halide photograph described in (1) above, in which one is also selected.
photosensitive material. (1) R-3○, S-M (II) ) Ma -So 2 S-R'(I
II) RSO2S I-m SS○ -R2
In the formula, R, R' and R2 may be the same or different, and
Represents an aliphatic group, aromatic group, or heterocyclic group, M is a cation
represents the I2 represents a divalent linking group, m is 0 or 1
It is. The compound of formula (1) or I■) is represented by (1) or T
Remanipulating the divalent group derived from the structure shown in JI)
There may also be a polymer contained as a position. Also possible
When R, I, R2, 1, combine with each other to form a ring.
may be completed. (3) The silver halide emulsion described in (1) above is halogenated.
It is characterized by being reduced sensitized during the process of forming root particles.
A silver halide photographic light-sensitive material. , (4) on the support
Halo having at least one halo-1 saponified emulsion layer
contained in the emulsion layer in silver germide photographic sensitization) A material
HI′: 1 silver generide grains are mainly from the (], 1.1.) plane
of the total projected area of silver halide grains.
More than 60% of the grains are tabular grains with an aspect ratio of 3 or more.
dislocations are concentrated near the apex of the particle, and the dislocations are concentrated near the apex of the particle.
Oxidizing agents for silver are added to the manufacturing process of silver halide emulsions.
A silver halide photographic material characterized by: (5) The oxidizing agent for silver has the formula (1), (II), or (
Select at least one compound from the compounds shown in III)
The silver halide photographic material described in (4) above
. (1) R-3(')2S-, -M(]II
R-3o2 SR'(II) RS 02
S L m-3S O2-R2 In the formula, R, R'
, R2 may be the same or different, and may be an aliphatic group or an aromatic group.
, or a heterocyclic group, and M represents a cation. [,teeth
It represents a divalent linking group, and m is 0 or 1. Compounds of formulas (1) to (III) include (1) to (
Repeating the divalent group derived from the structure shown in III)
It may also be a polymer containing it as a unit. Also possible
In this case, R, R', R2, and L combine with each other to form a ring.
may be completed. (6) The silver halide emulsion described in (4) above or a silver halide emulsion
It is characterized by being reduced sensitized during the process of forming root particles.
A silver halide photographic light-sensitive material. (7) Silver contained in the silver halide emulsion described in (4) above.
The vicinity of the surface of the rogenated root grain contains 5 mol% or more of silver iodide.
A halogen characterized in that it is made of silver halide.
silver oxide photographic material. (8)'' - Silver halide emulsion described in (7) or halogen
It should be noted that reduction sensitization occurs during the second stage of silver oxide grain formation.
Characteristic silver halide photographic materials. (9) The support contains at least one silver halide emulsion layer.
In a silver halide photographic light-sensitive material containing
The silver halide grains are mainly composed of (111) planes.
It is a normal crystal grain with dislocations concentrated near the apex of the grain.
The production process of silver halide emulsions involves the use of acids against silver.
Silver halide photographic effect characterized by the addition of a curing agent
light material. (10) The oxidizing agent for silver is of formula (1), (II), or
Select at least one compound from (III)
The known silver halide photographic material described in (9) above
. N) R-3o2S-M (U) )? -SO2S-R' (III) RSO□S-Lm-SSO2-R2 formula
Inside, R, R', and R2 may be the same or different, and fat
Represents a group group, aromatic group, or heterocyclic group, M is a cation
represents. L represents a divalent linking group, m is O or 1;
Ru. The compound of formula (1) or I[[) is a compound of formula (1) or I[[).
Repeating the divalent group derived from the structure shown in III)
It may be a polymer contained as a unit. Also possible
In this case, R, R', R2, and L combine with each other to form a ring.
may be completed. (11) Contained in the silver halide emulsion described in (9) above
The size distribution of silver halide grains has a coefficient of variation of 25% or less
Silver halide photographic effect characterized by having monodispersity
light material. 02) The silver halide emulsion described in (9) above contains halogen
It is characterized by being reduced sensitized during the process of forming silveride grains.
A silver halide photographic light-sensitive material. achieved by. The present invention will be explained in detail below. Silver halide grains contained in the silver halide emulsion of the present invention
(hereinafter also simply referred to as "particles") are mainly (111) planes
It is composed of Preferably 60% or more of the surface area of the particles
Above, more preferably 80% or more is due to (111) plane
It's working. One of the preferred shapes of silver halide grains for the present invention
are tabular grains. Here, the tabular silver halide grains are
, a halo with one twin plane or two or more parallel twin planes
It is a general term for silver germide grains. A twin plane is a (III) plane with all lattice points
When the ions have a mirror image relationship, this (Ill) plane
means. These tabular grains are triangular when viewed from the −
Shape, hexagonal shape or rounded circular shape
The triangular shape is triangular, and the hexagonal shape is triangular.
is a hexagonal shape, and a circular shape is a circular shape whose outer surfaces are parallel to each other.
It has a surface. In the present invention, preferred particle shapes have an aspect ratio of 3 or more;
Preferably, they are tabular grains of 3 or more and 8 or less. In the present invention, when referring to the aspect ratio of tabular grains,
Regarding tabular grains having a grain diameter of 0.3 μm or more
, each refers to the value obtained by dividing the particle diameter by the thickness. particle thickness
The measurement of the particle size is carried out with the latex as a reference.
Metal is deposited from the opposite direction, and the length of the shadow is measured using an electron microscope.
Measure in the photo 2 and refer to the length of the latex shadow
This can be easily done by calculating as follows. In the present invention, the particle diameter refers to the projection of the parallel outer surfaces of the particle.
It is the diameter of a circle with an area equal to the shadow area. The projected area of particles is determined by measuring the area on an electron micrograph.
Obtained by correcting the photographic magnification. The diameter of the tabular grains is 0.3 to 5.0 μm.
is preferable. The thickness of tabular grains is 0.05 to 0.
．． Preferably, the thickness is 5 μm. The tabular grains of the present invention occupy a preferable proportion in the emulsion.
60 out of the total projected area of silver halide grains in the emulsion
%, particularly preferably 80% or more. Furthermore, these
The average aspect ratio of tabular grains occupying a certain area of
The above is preferable. In addition, monodisperse tabular grains are used.
More favorable results may be obtained if Monodisperse
The structure and manufacturing method of tabular grains are disclosed in, for example, JP-A-63-
151618 etc., but the shape is simplified
In other words, 70% or more of the total projected area of silver halide grains.
is the maximum length for the length of the side with the minimum length.
A hexagon with a side ratio of 2 or less, and a flat
A flat plate having two horizontal surfaces as the outer surface.
Furthermore, the hexagonal plate-like halogen
Coefficient of variation of grain size distribution of silver oxide grains [its projection plane]
Size expressed by the yen-equivalent diameter of the product 1) Variation in child size
(Hani, which is the standard 71 (deviation) divided by the average particle size) is 2
It has a monodispersity of 0% or less. Preferred order for the present invention = 1 Genized root nodules of one shape
One is normal crystal grains. The area ratio of the (11,1) plane is
Tall particles exhibit an octahedral shape. (11,1)
Particle Q and other surfaces may coexist, or less than 40%, and
It is preferable that the G stiffness is 20% or less. The present invention can be applied even in the case of particles whose shape is difficult to specify (11,1
,) is effective if the surface ratio is high and the m point is clear.
Ru. Furthermore, the emulsion grains of the present invention have dislocations. Dislocations of tabular grains are caused by, for example, the above-mentioned J, F, lIamil
tons. Phot, Sci, Eng, +, u, 57, (
1967) and T, Shioz8wa. J, Soc, Phot, Sci, Japan, 35
．． 2] 3, (1972), transmission type electron transfer at low temperatures.
It can be observed directly using a microscope.
Wear. In other words, the pressure is so high that dislocations occur from the emulsion to the grains.
Silver halide grains taken out with care not to apply force
was placed on a mesh for electron microscopy to prevent damage caused by the electron beam.
Cool the sample to prevent scratches (pudding out, etc.).
observation using the transmission method. In this case the particle thickness
The thicker the electron beam, the more difficult it is for the electron beam to pass through.
2 (more than 10 kV) electrons for a particle with a thickness of 25 μ
It can be observed more clearly using a microscope. From photographs of particles obtained by this method, the main plane
Dislocations for each particle when viewed perpendicular to
The position of can be found. In the halogenated root particles of the present invention, dislocations are located at the apex of the particle.
concentrated in the vicinity. Here, dislocations are concentrated near the apex and
This means that the dislocation density near the apex is higher than that of other peripheral parts of the particle.
In other words, it is higher than the center. Preferably the dislocation density is
2 times or more, more preferably 4 times, particularly preferably 10 times
That's more than double that. The vertex can be easily identified if the particle has a polygonal shape.
Can be determined. Also, if the particles are rounded, it is somewhat ambiguous.
However, even in this case, if we draw a tangent to the outer circumference,
6TrA, which allows you to find vertices more easily, the vicinity of a point is a grain
115 to 1 of the diameter of the circle equivalent to the child projected area. / 1.0
When a sphere centered at each vertex is drawn with a radius corresponding to
say the inner area of In the case of a particle having multiple (II) vertices, each vertex's
It is sufficient if the dislocations are concentrated in the vicinity. Among n vertices,
It is not necessary that all vertices are dislocated or concentrated; at least one
The effect of the present invention can be obtained even if dislocations are concentrated near vertices.
It will be done. The oxidizing agent for silver of the present invention is an oxidizing agent for silver that acts on metallic silver and causes harmful effects.
Refers to a compound that has the effect of converting Especially ha
Extremely fine particles produced as a by-product during the formation process of silver halide grains.
Compounds that convert small silver atoms into radical ions are effective.
be. The root ions generated here are silver halide, sulfide
Silver salts, such as silver and silver selenide, which are poorly soluble in water may be formed,
Further, a water-easily soluble silver salt such as silver nitrate may be formed. Oxidizing agents for grudges can be inorganic or organic.
You can. Inorganic oxidizing agents include ozone and hydrogen peroxide.
and its adducts (e.g., Na BO2' H202
' 3Hz 0,2Na2 CO3・31(z 02
, Naa P207 ・2H202,2Naz SO
4・H202・2H20), peroxyalt salts (e.g.
, K2 S20B , K2 C20h, K2 P20B
), peroxy complex compounds (e.g. Kz [T
r (O□)C2O4) ・31 (2S on 20,4
04 ・Ti(O□)0■4・SO4・2HzO1Na
z I:VO(02)(CzOA)z ・6H20
], permanganate (e.g. KMnO4), chromic acid
Oxygen salts such as salts (e.g. K2 Cr 207 ), salts such as salts and bromine
Which halogen elements, perhalates (e.g. periodic acid)
potassium), salts of high valent metals (e.g. hexasia
potassium ferric acid) and thiosulfonate, etc.
be. In addition, as organic oxidizing agents, quinones such as p-quinone
, organic peroxides such as peracetic acid and perbenzoic acid, and activated halogens.
Compounds that release
, chloramine T1 chloramine B) are mentioned as examples.
. Preferred oxidizing agents of the present invention include ozone, hydrogen peroxide and
Its adducts, halogen elements, inorganic thiosulfonates
It is an oxidizing agent and an organic oxidizing agent of quinones. A more preferred oxidizing agent is a thiosulfonate, with the formula
Select from compounds represented by (I) to (III)
be able to. Among these, the most preferred is represented by formula (I).
It is a compound that is When silver is present, thiosulfonic acid converts silver using the reaction formula below.
Oxidation to form silver sulfide was described by S. Gahler.
Veroff wiss, Photolab Wo
lfen X, 63 (1965). RSO□SM+2Ag-+RSO□M+AgzS this way
It has been experimentally confirmed that oxidation is occurring.
Ru. (I) R-SO2S-M (I[) R-SO□ S-R' (III) RSO2S Lm 5SO2R
``In the formula, RXR' and R2 may be the same or different,
Represents an aliphatic group, an aromatic group, or a heterocyclic group, and M is an cation.
Represents on. L represents a divalent linking group, m is 0 or 1
It is. Compounds of general formulas (1) to (III) include (1)
Repeating the divalent group derived from the structure shown in 1)
It may be a polymer contained as a unit. Also possible
When R, R1, R2, , R2, and L are combined with each other,
It may form a ring. Thiosulfates of general formulas (1), (II) and (III)
To explain the phonic acid compounds in more detail, R1R1 and
When R2 is an aliphatic group, saturated or unsaturated, straight chain, branched
or cyclic aliphatic hydrocarbon group, preferably carbon
Alkyl group with prime number 1 to 22, carbon number 2 to 22
Alkenyl group, alkynyl group, these are substituents
It may have. As an alkyl group, for example, methyl
, ethyl, propyl, butyl, pentyl, hexyl,
Octyl, 2-ethylhexyl, decyl, dodecyl, hexyl
Xadecyl, octadecyl, cyclohexyl, isopro
Examples include pill, t,-butyl. Examples of alkenyl groups include allyl and butenyl.
It will be done. Examples of alkynyl groups include propargyl, butynyl
can be given. The aromatic groups for R, R' and R2 are monocyclic or fused rings.
aromatic group, preferably having 6 to 20 carbon atoms.
Examples include phenyl and naphthyl. this
These may be substituted. The heterocyclic group of R, R' and R2 includes nitrogen, oxygen,
At least one element selected from sulfur, selenium, and tellurium
and having at least one carbon atom
It is a 15-membered ring, preferably a 3- to 6-membered ring.
For example, pyrrolidine, piperidine, pyridine, tetra
Hydrofuran, thiophene, oxazole, thiazole
, imidazole, benzothiazole, henzoxazole
Benzimidazole, Selenazole, Benzoselenium
Zole, Tetrazole, Triazole, Benzotriazo
ole, tetrazole, oxadiazole, thiadeazole
A ring can be given. Examples of substituents for R, R' and R2 include alkyl groups.
(e.g. methyl, ethyl, hexyl), alkoxy groups
(e.g. methoxy, ethoxy, octyloxy),
lyl groups (e.g. phenyl, naphthyl, tolyl),
droxy group, halogen atom (e.g. fluorine, chlorine, bromine)
, iodine), aryloxy groups (e.g. phenoxy), aryloxy groups (e.g. phenoxy),
alkylthio groups (e.g. methylthio, butylthio),
lylthio group (e.g. phenylthio), acyl group (e.g.
(e.g., acetyl, propionyl, butyryl, valeryl)
, sulfonyl groups (e.g. methylsulfonyl, phenyl
sulfonyl), acylamino groups (e.g. acetylamino),
, benzoylamino), sulfonylamino groups (e.g.
, Methanesulfonylamino, Henzensulfonylamino
), acyloxy groups (e.g. acetoxy, benzoxy)
, carboxyl group, cyano group, sulfo group, amino group, -
3o2SM group, (M represents a monovalent cation) -3o2
Examples include R' group. The divalent linking group represented by is C, N, S and
an atom or atomic group containing at least one species selected from
It is. Specifically, alkylene groups, alkenylene groups,
lunitonylene group, arylene), (, -〇-1-S-1
-NH-1-CO-1-SO□-, etc. alone or this
It consists of &J+combination of et al. 1 is preferably a monovalent aliphatic group or a divalent aromatic group.
It is. ■, is a monovalent aliphatic), (for example, (C
H2+7 (II is 1 to 12), C112-CH=(II-CH2-1 -CIi2C3CCI7-).As the divalent aromatic group for L, for example,
Examples include phenylene group and naphthylene group. These substituents can be further substituted with the substituents mentioned above.
It may be M is preferably a metal ion or an organic cation.
Ru. Examples of metal ions include lithium ions, NaI
- Lithium ions and potassium ions are mentioned. organic mosquito
Examples of thione include ammonium ion (ammonium ion).
um, TeI-ramethylammonium, Tetrabutylammonium
monium, etc.), phosphonium ion (tetraphenylphonium, etc.), phosphonium ion (tetraphenylphonium, etc.)
sulfonium) and guanidyl groups. - When Noshiro (1) to (III) is a polymer
, the following are examples of repeating units:
Ru. -(-CHClI2 + CO□CtlzCt120CIIzCHzSOzS
, CH3 ■ -(-C-C11□-)- Co2 CH2C1(□ S-302R C1l. --(-C-C1(2→- SO□SM) These polymers may be homopolymers or other copolymer
A copolymer with a polymerizable monomer may also be used. -Compound represented by Noshiro (1), (II) or (III)
Specific examples of products are listed in Table A below, but are not limited to these.
It doesn't mean that it will happen. Compounds of general formulas (I), (II) and (1) are
1972-1019, British Patent No. 972.211;
Journal of Organic Chemist
ry (Journal of Power 7 Nick Chemi)
Volume 53, page 396 (1988) and Che
chemical abstracts
59, 9776e.
It can be easily synthesized using the following method. The amount of oxidizing agent added to 1 mole of silver in the present invention is from ]07
It is desirable to select from the range of 10-1 mol. Preferably
10-''' mole to 10-2 mole, more preferably
10-5 moles to 10-'' moles. Upon addition of oxidizing agent.
The period is during the manufacturing process of silver halide emulsion, and grain formation is in progress.
, after particle formation, desalting and redispersion process, during chemical sensitization
, or may be added at any time after the completion of chemical sensitization. Special
During grain formation, preferably after the completion of one grain formation, chemical sensitization is carried out.
It can be added before or during the process. -Production process of oxidizing agents represented by Noshiro (1) to (1m)
When adding additives to photographic emulsions,
Methods commonly used can be applied. For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water should be treated with a suitable water-miscible compound.
A solvent such as alcohols, glycols, keto
Among the compounds, esters, amides, etc., those with photographic properties
Dissolve in a solvent that does not have a negative effect, and add it as a solution.
can be done. The silver halide emulsion of the present invention is used during and after grain formation.
and before or during chemical sensitization, or during chemical sensitization
It is preferable to carry out reduction sensitization afterwards. Here, reduction sensitization refers to adding a reduction sensitizer to a silver halide emulsion.
A method of adding pAg I to 7 (low 1) called silver ripening
Method of growing or aging in an atmosphere of b, high p
++In an atmosphere with a high pH of pl+8 to 11, which is called maturation.
Choosing either growing or ripening method
I can do it. It is also possible to use two or more methods together.
. The method of adding a reduction sensitizer allows you to finely adjust the level of reduction sensitization.
This is a preferable method because it can be adjusted. As reduction sensitizers, stannous salts, ascorbic acid and their
Derivatives, amines and polyamines, hydrazine derivatives
, formamidine sulfinic acid, silane compounds, borane
Compounds and the like are known. These known reduction sensitizers are selected for the reduction sensitization of the present invention.
It is also possible to use two or more compounds together.
Can also be done. Stannous chloride, thio dioxide as reduction sensitizers
Urea, dimethylamine borane, ascorbic acid and
Derivatives of are preferred compounds. Addition amount of reduction sensitizer
depends on emulsion manufacturing conditions, so it is necessary to select the amount added.
is lo-7 to 10-3 mol per mol of silver halide.
The range is appropriate. Reduction sensitizers include water, alcohols, glycols,
Particles dissolved in solvents such as ketones, esters, amides, etc.
Added during child growth. Add to reaction vessel
However, it is preferable to add it at an appropriate time of grain growth.
Yes. Also water-soluble silver salt or water-soluble alkali halide
A reduction sensitizer is added in advance to an aqueous solution of
Even if silver halide grains were precipitated using an aqueous solution of
good. In addition, as the particles grow, the reduction sensitizer solution is added several times.
It is also preferable to add it in parts or continuously over a long period of time.
This is a good method. Silver halide grains of the present invention, preferably aspect ratio 3
The above tabular grains contain 5 mol% or more of silver iodide near the surface.
B is preferably made of silver halide containing B. Contains silver iodide content near the grain surface.
Various methods known in the past as methods for trolling
Can be adopted. Growth in the presence of JW colloids
An aqueous solution of a water-soluble root salt is added to the silver halide grains.
and adding an aqueous solution of a halide containing a water-soluble iodide.
method; adding an aqueous solution of halides containing water-soluble iodides.
Adding method: Adding poorly soluble iodine such as silver iodide or silver iodobromide
You can choose from methods such as adding chemicals and aging.
Wear. Alternatively, iodide-containing silver halide grains are
By physical ripening, iodide is distributed even near the surface.
It is also possible to use a method such as Silver iodide contained near the surface of the silver halide grains of the present invention
is preferably as uniform as possible on the surface. of particles
A layered structure whose entire surface is covered with a layer containing silver iodide.
It is preferable to take However, 111) and (110)
Grains such as tetradecahedrons with coexisting faces or tabular grains
For particles with both principal planes and side surfaces, a specific plane
is covered by a layer containing mainly silver iodide
is also a preferred form of the present invention. In other words, the entire surface of the particle
If the layer is partially covered with a layer containing silver iodide,
Both cases belong to the present invention. Forming a layer containing 5 mol% or more of silver iodide near the surface of the present invention
Spectral sensitization of cyanine, merocyanine, etc.
Pigments or mercapto compounds, azole compounds, aza
Presence of anti-fog agents/stabilizers such as indene compounds
The preferred method is to Similarly, thiocyanate and thiocyanate
Contains silver halide solvents such as ether, ammonia, etc.
It may also be preferable to have it present. The silver iodide content near the surface of the silver halide grains of the present invention is
can be detected by means of elemental analysis of each surface. XPS・
Using methods such as Auger electron spectroscopy and ISS
Useful. XP is the simplest and most accurate method.
S (X-ray Photoelectron
5 pectroscopy), and the surface of the present invention
Neighboring silver iodide content is defined by measurements using this method.
It can be done. X P S (X-ray Photoelect
ron 5 pectroscopy) surface analysis method.
The depth that can be analyzed is said to be about 1oλ. Used for analysis of iodine content near the surface of silver halide grains.
Regarding the principles of the XPS method, Atsushi Aihara et al.
Son's spectroscopy 1 (Imori Library 16, published by Kyofu Publishing,
1973) is a standard measurement method that uses M as an excited X-ray.
g-) Halogenation using α and appropriate sample form
Photoelectricity of iodine (1) and roots (Ag) released from silver particles
The strength of the child (usually l-3d, /□, 8g-36sz□)
This is a method of observing the degree of To determine the iodine content, the iodine content is known
Using several types of markers (1), Tatsumoto (1) and roots (Ag
) Test of the photoelectron intensity ratio (intensity (I) 7 intensity (8 g))
It can be determined by creating a calibration curve and using this calibration curve. C
In silver halide emulsions, zeolite adsorbed on the surface of silver halide grains
After decomposing and removing latin with proteolytic enzymes,
P S measurements must be made. The grain surface of the present invention contains 5 mol% or more of silver iodide near its surface.
Silver halide grains are emulsion grains contained in one emulsion.
When analyzed by means of elemental analysis near the surface, iodine was detected.
Refers to silver content of 5 mol% or more. In this case, bright
If two or more emulsions are clearly mixed, centrifuge
After applying appropriate pretreatment such as separation method and filtration method,
It is necessary to analyze the emulsion. More preferably XP
When the standard measurement of S is carried out, the silver iodide content is 5 to 3.
Refers to a 0 mol% emulsion. The effect of the present invention is that the silver iodide content near the surface of the grains is 5 mol% or more.
It is noticeable when containing 7.5 mol near the surface.
% or more, more preferably 10 to 15 mol% near the surface
These are grains containing silver iodide. The halogen composition near the surface other than silver iodide is preferably odor-free.
Although it is silver chloride, it must contain 10 mol% or less of silver chloride.
You can also do it. The effects of the present invention can be achieved in both monodispersed emulsions and polydispersed emulsions.
However, silver halide grains are mainly composed of (111,) planes.
In the case of normal crystal particles, monodisperse porosity particles are more
preferable. Here, monodisperse means a variation in the equivalent sphere diameter of the particle volume.
It was defined by the coefficient being 25% or less. more preferred
or less than 20%, particularly preferably less than 15%.
be. The silver halide grains t used in the present invention include tN bromide, silver chloride,
Silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide
be. Other silver salts, such as rotane silver, silver sulfide, and
silver ion, silver carbonate, silver phosphate, and organic acid silver as separate particles.
Even if it is included as part of silver halide grains,
good. Rapid development and desilvering (bleaching and bleach-fixing) processes
silver halide with a high silver chloride content when it is desired to
Particles are preferred. Also, when suppressing development moderately,
preferably contains silver iodide. Preferred silver iodide content
The amount varies depending on the desired photosensitive material. For example, the X-ray feeling
0.1 to 15 mol% for wood, Graphisoquarts and
For microsensitive materials, the preferred range is 0.1 to 5 mol%.
Ru. This is preferable for photographic materials such as color negatives.
Silver halide containing 1 to 30 mol% silver iodide
and more preferably 5 to 20 mol%, particularly preferably
The content is 8 to 15 mol%. Silver iodobromide grains contain silver chloride.
In some cases, it has the effect of relaxing lattice strain.
More preferred. The silver halide emulsion of the present invention has halogen groups in its grains.
It is preferable that the composition has a distribution or structure. Typical examples are JP-B No. 4343162 and JP-A No. 6
1-215540M, JP-A-60-22284.5,
JP-A-60-143331, JP-A-61-7533
7 - The interior and surface layers of particles as disclosed in bows etc.
Core-shell type or single type with different halogen compositions
It is a double-structured particle. In addition, it is not just a double structure,
Three such as disclosed in Japanese Patent Application Laid-open No. 60-222844.
Multi-layered structure or more multi-layered structure,
A 5'-silver composition is applied to the surface of Ko-Shell's double-structured particles.
It is possible to thinly coat the silver halide containing the silver halide. In order to give a structure to the inside of a particle, it is necessary to enclose it as described above.
In addition to the bonding structure, it also connects particles with a so-called bonding structure.
I can come. These examples are published in Japanese Patent Publication No. 59-1335.
No. 40, JP-A-58-108526, European Patent No. 1.
No. 99.29OA2, Special Publication No. 58-24772, Japanese Patent Application Publication No. 58-24772
It is disclosed in Sho 59-16254 and the like. join
The crystal has a different composition from the host crystal.
Produced by bonding to edges, corners, or surfaces of crystals
can be done. This type of bonded crystal is called a boss crystal.
Even if the halogen composition is uniform or the core
Even if it has a shell-type structure, it can be formed.
I can do it. In the case of bonded structures, the combination of silver halides is of course
It is possible, but it is not a rock salt structure such as Rodan silver or silver carbonate.
By combining a silver salt compound with a silver halide to form a bonded structure.
I can do it. Non-silver salt compounds such as lead chloride can also be used in bonding structures.
It may be used if it can be constructed. In the case of grains such as silver iodobromide having these structures, the core part
It is preferable that the silver iodide content is higher than that of the shell part.
This is a new aspect. On the other hand, the silver iodide content in the core is low and the
Particles with high wells may be preferred. Similarly, the joint structure
Even for grains with a structure, the silver iodide content of the host crystal is
The silver iodide content of the bonded crystal is relatively low.
or vice versa. Also, these
The boundary parts of structured particles with different halogen compositions are
The boundary may be clear or unclear. It is also preferable to actively change the composition continuously.
It is a mode. Two or more silver halides as a mixed crystal or with different structures
In the case of existing silver halide grains, halos between the grains
It is important to control the gene composition distribution. between particles
Regarding the measurement method of rogen composition distribution, JP-A-60-254
It is described in No. 032. Uniform halogen distribution between particles is a desirable characteristic
It is. In particular, highly uniform emulsions with a coefficient of variation of 20% or less are
preferable. Another preferred form is particle size and halogen combination.
It is an emulsion that has a correlation with its composition. For example, large-sized particles have a high iodine content;
Size may be correlated with low iodine content.
Ru. Depending on the purpose, there may be a reverse correlation, or a correlation with other halogen compositions.
You can choose. Two different compositions for this purpose
It is preferable to mix the above emulsions. The silver halide emulsion used in the present invention is European Patent No. 96.7.
Disclosed in No. 27B1, No. 64,412B1, etc.
A process that brings roundness to particles, or a West German patent
No. 2,306.447G2, JP-A-60-22132
The surface may be modified as disclosed in No. 0.
. Generally, the particle surface has a flat structure, but it is intentionally made uneven.
It is preferable in some cases to form a JP-A-58-106532, JP-A-60-22132
A part of the crystal described in No. 0, such as the apex or
The method of drilling a hole in the center of the surface or the method described in U.S. Patent No. 4.
The ruffle particles described in No. 643,966 are
This is an example. The grain size of the emulsion used in the present invention was determined using an electron microscope.
Calculated from the circle equivalent diameter of the projected area, projected area and particle thickness.
Sphere-equivalent diameter or Coulter counter of particle volume
It can be evaluated using the equivalent sphere diameter of the volume according to the method. spherical phase
From ultrafine particles with an equivalent diameter of 0.05 microns or less, 1
Select and use from coarse particles exceeding 0 microns.
I can do it. Preferably 0.1 micron or more and 3 microns
Use the following grains as photosensitive silver halide grains
It is. In addition, in order to satisfy the target gradation of photosensitive materials,
Grain size in emulsion layers with qualitatively identical color sensitivity
Two or more types of monodispersed silver halide emulsions with different characteristics are placed in the same layer.
Can be mixed or applied in separate layers. 2 more
Polydisperse silver halide emulsions or monodisperse emulsions of more than one type
Used by mixing or layering a combination of and polydisperse emulsion.
You can also. The photographic emulsion used in the present invention is described in "Photography by Graffkide".
"Physics and Chemistry", published by P. Glafkides, Chimie et Phys
ique PhotographyjquePaul M
ontel, 1967), Duffin, “Photographic Emulsion Chemistry”
”, published by Focal Press (G, F, Duffin, P
photographicEmulsion Chemi
try (Focal Press+ 1996
), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
Published by Karpeles (V, L, Zelikman et a
l, Making andf'; oatinB ['
photographic emulsion, Foc
af Press. It can be prepared using the method described in 19 [i4) etc.
You can do something like that. i.e. acid method, neutral method, ammonia method
etc., and soluble 11 (salt and soluble halo) may be used.
One-sided mixing method and simultaneous mixing are methods for reacting Gen salts.
You may use any method such as a method or a tilted platform. Method of forming particles by exposing them to -F containing excess silver and ions
(so-called back mixing method) can also be used. simultaneous mixing
In the liquid phase, silver halide is formed as two forms of the method.
The method of keeping 96g constant, that is, the so-called Con I・
You can also use the rolled, double ji ry l method.
Ru. According to this method, the crystal shape is regular and the grain size is
A nearly uniform silver halide emulsion can be obtained. Halogen precipitated in reaction vessel for emulsion preparation
Method of Adding Silver Bide Grains, U.S. Patent No. I, 334,
No. 012, i, 301,241, 4, 1.
50.994 Preferred in some cases. These are seeds
It can also be used as a silver halide crystal for growth.
It is also valid if the particle is supplied as
- It is preferable to add a small emulsion of
Addition methods include adding the entire amount at once, or dividing it into multiple additions.
The water can be added continuously, etc.
I can do it. In addition, various types of halo are applied to modify the surface.
It may be effective in some cases to add particles with a composition of
be. Most or very little of the halogen composition of silver halide grains
The method of converting a portion using the halogen conversion method is in the United States.
Patent No. 3.477.852, Patent No. 4,14.2,9 (1
0, European Patent No. 213.429, European Patent No. 273,430
, disclosed in West German Published Patent No. 3.81.9,241 etc.
It is an effective particle formation method. Less soluble silver salts
Is it possible to convert to ? Yo 1 student from Haroken? b, or
Silver halide grains can be added. −・degree
Convert, convert in multiple steps, or continuously
You can choose from methods such as converting to . Soluble silver salts and halogens at constant concentration and constant flow rate for particle growth
In addition to the method of adding salt, British Patent No. 1.469,48
No. 0, U.S. Patent No. 3,650,757, U.S. Patent No. 4.242
．． Varying the concentration as described in No. 445,
A particle formation method that changes the flow rate is a preferred method.
It is. Increase the concentration or increase the flow rate
By doing so, the amount of halogenated roots supplied can be increased by 11 hours.
A linear function of , a function of , or a more complex function changes
can be done. It is also possible to reduce the amount of silver halide supplied if necessary.
It is preferable depending on the situation. Furthermore, multiple i with different solution compositions
Adding iJ soluble silver salt or adding a compound with different solution composition.
Increase one when adding several soluble halokene salts
Addition methods that reduce and eliminate the one and the other are also effective.
It's a method. A solution of I-IJ soluble silver salt and soluble halogen salt is reacted.
- Mixer for heating is U.S. Pat. No. 2.996.287;
3, 342.605, 3,4], 5,650
No. 3,785,777, West German Published Patent No. 2,556
＋885 and 2,555,364.
You can use any of the following methods. For the purpose of promoting ripening, there is a 7halogenide solvent.
It is for use. For example, ν) an excessive amount of halogen to promote growth.
It is known that there is a rebellion against the ion, and that there is a problem in the vessel. Other ripening agents can also be used.
. Adding silver and halide salts to these ripening agents
The entire amount can be blended into the dispersion medium in the reactor beforehand.
If you add shreds, halide salts, silver salts or deflocculants
They can also be introduced into the reactor together. With another variant
The ripening agent is then uniquely treated with a halide salt and silver salt addition step.
It can also be installed standing up. Ammonia, thiocyanate (Rhodankali, Ni) Dana
organic thioether compounds (e.g.
U.S. Patent Nos. 3,574,628 and 3,021,21
No. 5, No. 3,057,724, No. 3.038.80
No. 5, i, 276.374, 4,297,43
No. 9, No. 3,704,130 No. 1, No. 4,782.
No. 013, JP-A No. 57-1.04926, etc.
Compound. ), 1,000-ion compounds (for example, JP-A-53-824
No. 08, No. 55-77737, U.S. Patent No. 4,221
, 86.3 Tetrasubstituted thiourea and others described in
, a compound described in JP-A-53-144319
), and the ha
Mercap I compound that can promote the growth of silver lokenide grains
compounds, amine compounds (e.g. JP-A-54-1 (10717)
number, etc.). As a protective colloid used in preparing the emulsion of the present invention
, and other hydrophilic colloid layer bangu
, it is advantageous to use gelatin, but other hydrophilic
Sex colloids may also be used. For example, gelatin derivatives, graphinization of ceratin with other polymers, etc.
F1 ~ Proteins such as polymers, albumin, and casein; human
1: Roxyethyl cellulose, carboxymethyl cellulose
Cellulose inducers such as cellulose, cellulose sulfate, etc.
conductors, sodium alginate, sugar derivatives such as starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partially acetic acid
Tar, poly-N-vinylpyrrolidone, polyacrylic acid
, polymethacrylic acid, polyacrylamide, polyvinyl
Single or imidazole, polyvinylpyrazole, etc.
The use of various synthetic hydrophilic polymer materials such as copolymers
I can do it. In addition to lime-processed gelatin, acid-processed gelatin is also used.
Chin, Bull, Soc, Sci, Photo,
Japan. No, 16. As described in P2O (1966)
Enzyme-treated gelatin may be used, and gelatin addition may also be used.
Hydrolyzed products and enzymatically degraded products can also be used. The emulsion of the present invention is washed with water for desalting and freshly prepared
It is preferable to use protective colloid dispersion. The temperature for washing with water is stated depending on the purpose, but it is between 5° and 50°C.
It is preferable to choose within a range. The pH during washing also depends on the purpose.
You can choose between 2 and 10, but it is preferable to choose between 2 and 10. moreover
Preferably it is in the range of 3-8. The pAg during washing can be selected depending on the purpose, but it should be between 5 and 10.
It is preferable to choose. Noodle washing method as a washing method
, dialysis method using semipermeable membrane, centrifugation method, coagulation sedimentation method,
The on-exchange method can be selected and used. coagulation
In the case of precipitation method, sulfate is used, organic solvent is used.
methods using water-soluble polymers, gelatin derivatives
You can choose from methods such as using . When preparing the emulsion of the present invention, for example, during grain formation, desalting process, chemical
When sensitizing, it is not possible to have metal ion salts present before application.
Preferable depending on purpose. When doping particles,
During formation, modification of particle surface or used as chemical sensitizer
It is preferable to add it after grain formation and before the end of chemical sensitization.
Delicious. When the entire particle is doped and when a part of the core of the particle is doped.
or only the shell part, or the evixial part
You can also choose to dope the base particles or dope them into the base particles.
Ru. Mg, Ca, Sr, Ba, Δn, Sc. Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn
, , Ga, Ru, Rh, Pd, Re, Os. T r, P t, , Au, , Cd, Hg, T1. , In
. Sn, Pb, Bi, etc. can be used. these
Metals include ammonium salts, acetates, nitrates, sulfates, and phosphoric acids.
Particle forms such as salts, hydroxides, 6-coordination complex salts, 4-coordination complex salts, etc.
It can be added as long as it is in the form of a salt that can be dissolved at the time of formation.
Ru. For example, CdB'rz, CdCL, Cd (No3
)2, Pb (No3)z, Pb (CH3COO
)2, K3 CF e (CN) 6), (NH4
) 4 (Fe (CN)b ), K3 1 rCρ6
, (NH4), RhC1,, K, Ru (CN
) 6 etc. As a glue gunt for coordination compounds
Ha0, Ako, Cyano, Cyanate, Thiocyanate, Ni
Trosyl, thionitrosyl, oxo, carbonyl
You can choose from. One type of these metal compounds
It may be used in combination, but two or three or more types may be used in combination.
It's okay to stay. The metal compound is water or an appropriate solution such as methanol or acetone.
It is preferable to add it by dissolving it in a suitable solvent. An aqueous hydrogen halide solution (e.g. HC
1, HBr etc.) or alkali halides (Example K
Cj2, Na C1l, KBr, , NaBr, etc.)
Additional methods can be used. Also, if necessary, use acid.
An alkali etc. may be added. Even if the metal compound is added to the reaction vessel before particle formation, the particle shape remains.
It can also be added during construction. Also, water-soluble root salts (e.g.
A g N 03) or aqueous alkali halide
Addition of halo to liquids (e.g. Na Cj2, KBr, KI)
It can also be added continuously during the formation of silver germide grains. difference
In addition, a solution independent of water-soluble root salts and alkali halides is added.
It may be prepared and added continuously at appropriate times during particle formation.
stomach. Furthermore, it is also preferable to combine various additive forces. Rice [(described in 1 Patent No. 3,772,031 υ)
Adding chalcogenide compounds during emulsion preparation
Strength may also be useful. S, S(!, except l' e,
QKomocyanate, thiocyanate, murenocyanic acid, carbonic acid
n1 phosphate, acetate (+', U, l,
stomach. The silver halide grains of the present invention are sulfur sensitized, -relene sensitized,
Gold sensitization, Balashira l1, sensitization or noble metal sensitization, reduction sensitization
At least one of the (
It can be applied in any step. Two or more sensitization methods
Combinations and combinations are preferred. At what stage do you chemically sensitize?
i+! ] To make
I can do it. A type that embeds chemical sensitization inside the particles.
, particles - type that embeds shallowly from the surface, or
There is a type that creates a chemical sensitization pattern on the surface. The emulsion of the present invention is
Depending on the purpose, you can choose a chemically sensitized location, but
-・General 6j It is preferable to have at least one type of chemical near the surface.
This is the case when I created a school sensitizer. One of the preferred chemical sensitizations that can be carried out in the present invention is carnivorous sensitization.
It is Chinese-German or a combination of 1genite sensitization and noble metal sensitization,
The Photog by James (I, 11. Jamcs)
Rough Process, 4th edition, published by Macmillan, 19
1977, (I, tl, James
ry of the Photographic Pro
cess, 4th ed, Macmillan. 1.977) Active enzyme as described on page 6, page 76.
It can be done using latin or research data.
Disclosure Volume 120, April 1974, 1.2 (
108. Research, Disclosure, Volume 34, 1975, 6
May, 13452, U.S. Patent No. 2.642.361
, No. 3,297,446, No. 3.772.031,
3,857,71.1, 3,901. ．． 714
No. 4,266.018, and No. 3,904,
No. 415, as well as British Patent No. 1,315,755.
pAg 5-10, pH 5-8 and temperature as listed.
Sulfur, selenium, tellurium, gold, at degrees 30-80 IC.
Platinum, palladium, iridium or a combination of these sensitizers
It can be a combination of numbers. In precious metal sensitization
, using noble metal salts such as gold, platinum, palladium, and iridium.
Among them, gold sensitization, palladium sensitization and
and a combination of both is preferred. For gold sensitization, gold chloride
Acid, potassium 1, potassium
Known materials such as lithiosia un-+-1 gold sulfide, gold selenaite, etc.
Compounds can be used. Palladium compounds are
Means divalent radium salt or tetravalent salt. Preferred path
The radium compound is R2PdX, or R2PdX,
It is expressed as Here R is a hydrogen atom, an alkali metal atom
Or represents an ammonium group. X represents a halogen atom
Represents a chlorine, bromine or iodine atom. Specifically, K21. )dCff4, (N14.)2P
dCL , Naz PdCL, (NH4)2PdC1,
,l,i. PdCf! , 4, Na, I'd (12t also
However, PdBra is preferred. gold compounds and rosera
J, the compound is thousocyanate or selenocyanate
It is preferable to use it together with. Hypo and thiourea compounds as sulfur sensitizers! -1ta
Nin-based compounds and US Specialty No. 3.857.711
, No. 4.266.018 and No. CO54,457
The sulfur-containing compounds described in
reactor. Chemical sensitization due to the presence of so-called chemical sensitization aids F
- Can also be done. Useful chemical sensitization aids include Asain Den
, azapyridazine, azapyrimidine, chemical sensitization
In the process, it suppresses fog and increases eye sensitivity.
Compounds known as such are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat. No. 2,1.31.
．． No. 038, No. 3.4LL91.4, No. 3,554,
No. 757, JP-A No. 58-1.26526 and the above-mentioned da
Finn [Photographic Emulsion Chemistry], pages 138-143.
It is. It is preferred that the emulsion of the present invention be used in combination with gold sensitization. stomach. The preferred amount of gold sensitizer is 1 mole of silver halide.
1X10-' to IX10-7 mol, and
Preferred values are 1X10'-5 to 5X1. O-7 mole
Ru. The preferred range of the palladium compound is from 1 x 10゜
It is 5X10-7. Thiocyanide or seleno
The preferred range of cyanide is 5 x 10-2 to 1 x 1
It is 07. In the present invention,
A sulfur sensitizer is used for silver halide 1×10
-4 ~ l
It is 1X10' to 5XIO-7 moles. Selenium sensitization is a preferred sensitization method for the emulsion of the present invention.
There is. In selenium sensitization, known unstable selenization
Specifically, colloidal metal selenium,
Selenoureas (for example, N5-J-dimethylselenourea)
, N,N-diethylselenourea, etc.), selenoketones,
Selenium compounds such as selenoamides can be used.
Ru. Selenium sensitization is sulfur sensitization, noble metal sensitization, or
It may be preferable to use both in combination. The photographic emulsion used in the present invention includes a photosensitive material manufacturing process.
, prevent fogging during storage or photo processing, or
contains various compounds for the purpose of stabilizing photographic performance.
can be done. Zunawara thiazoles, e.g.
Nzothiazoliu J, salt, 21-loimidazole, nit
lohenzimidazole, chlorobenzimidazole
, promohene imidazoles, mercaptothiazole
mercaptohenzothiazoles, mercaptohenz
・Imidazoles, mercap 1 to thiadiazoles, a
Minotriazoles, benzotriazoles, nitrobes
Inzotriazoles, mercaptotetrazoles (especially
1-phenyl-5-mercaptotetrazole);
Lucatopyrimidines; Mercaptotriazines; and
thioketo compounds such as oxadorinthione;
Indenes, such as triazaindenes, tetraaza
Indenes (especially 4-hydroxy-substituted (1,3,3a.7) tetraazaindenes), pentaazaindenes, etc.
What is known as antifoggant or stabilizer,
Many compounds can be added. For example, U.S. Pat. No. 3,954. ．． No. 174, 3.9
Described in No. 82.947 and Special Publication No. 52-28660.
can be used. One of the preferred compounds
There is a compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are added before, during, and after particle formation.
After particle formation, washing process, dispersion after washing, before chemical sensitization,
At various times during chemical sensitization, after chemical sensitization, and before application.
It can be added depending on the purpose. Added during emulsion preparation
In addition to exhibiting its original fog prevention and stabilizing effect,
, control the crystal habit of particles, reduce particle size,
Decrease solubility of dyes, control chemical sensitization, dye
It can be used for multiple purposes, such as controlling arrays. The photographic emulsion used in the present invention contains methine dyes and others.
Therefore, the effect of the present invention is achieved by spectral sensitization.
preferred. The pigments used include cyanine pigments, melon pigments,
Cyanine pigment, composite cyanine pigment, composite merocyanine color
dye, holopolar cyanine dye, hemicyanine dye,
Included are tyryl dyes and hemioxonol dyes. Particularly useful dyes include cyanine dyes, nocyanine dyes,
and a pigment belonging to complex merocyanine pigments. These pigments contain cyanine color as a basic heterocyclic nucleus.
Any of the nuclei commonly used for elementary classes can be applied. sand
That is, pyridine nucleus, oxazoline nucleus, thiozoline nucleus, pyridine nucleus,
roll nucleus, oxazole nucleus, thiazole nucleus, selenazole
le nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus
etc; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei;
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is,
Indolenine nucleus, benzindolenine nucleus, indole nucleus
, benzoxadol nucleus, naphthoxazole nucleus, ben
Zothiazole nucleus, naphthothiazole nucleus, henzoselenazo
Applicable to core nuclei, benzimidazole nuclei, quinoline nuclei, etc.
can. These nuclei may be substituted on carbon atoms.
stomach. Keto for merocyanine dyes or complex merocyanine dyes
Pyrazolin-5-one as a nucleus with methylene structure
nucleus, thiohydantoin nucleus, 2-thioxazolidine-2
, 4-dione nucleus, thiazolidine-2,4-dione nucleus,
- 5- to 6-membered heteromorphs such as danin nucleus and thiobarbic acid nucleus
A ring nucleus can be applied. These sensitizing dyes may be used alone, but a combination of them may be used.
Combinations of sensitizing dyes may also be used (in particular, combinations of sensitizing dyes are
Often used for emotional purposes. Representative examples are U.S. Pat. No. 2,688,545;
977゜229, 3, 397, 060, 3
, No. 522,052, No. 3.527.641, No. 3,
No. 617,293, No. 3, No. 628, No. 964, No. 3
．． No. 666, 480, No. 3.672.898, No. 3
．． No. 679.428, No. 3,703,377, No. 3,
No. 769,301, No. 3,814゜609, No. 3,8
No. 37,862, No. 4,026,707, Eida Patent No.
1. , 3/14.281, 1,507,803
, Special Publication No. 43-4936, 53-], 2.37
No. 5, Japanese Patent Publication No. 52-110.618, No. 52-109
, No. 925. Along with sensitizing dyes, colors that do not themselves have spectral sensitizing effects
A substance that does not substantially absorb elementary or visible light,
A substance exhibiting supersensitization may also be included in the emulsion. When adding a sensitizing dye to an emulsion, jvJ
At any stage of emulsion preparation known to be used for
You can. Most commonly after completion of chemical sensitization and before application.
U.S. Patent No. 3,628.9
No. 69, and No. 4.225. Described in issue C16G
Simultaneously with a chemical sensitizer as shown in II.
It is also possible to perform photosensitization at the same time as chemical sensitization.
i13,928 prior to chemical sensitization.
It can also be carried out standing up, and halogenated root particles-sedimentation can also be carried out.
It is also possible to start spectral sensitization by adding V' before the completion of generation.
Ru. Taught in U.S. Patent No. 4,225.666
Add these compounds in portions as described.
i.e. some of these compounds are added prior to chemical sensitization.
It is also possible to add the remaining amount after chemical sensitization.
Yes, disclosed in U.S. Patent No. 4,183.756.
At what stage during silver halide grain formation, including
It may be. The amount added is 4X10-' to 8 per mole of silver halide.
×10″ Can be used in 3 mol, but is more preferable
In the case of silver halide grain size 0.2 to 1.2 μm, approx.
5×10 −5 to 2×10 3 moles are more effective. The various additives mentioned above are used in the photosensitive materials related to this technology.
However, various additives can be added depending on the purpose.
Can be used. These additives can be found in more detail in the Research Disclosure.
Di+ Item 17643 (December 1,978
), same Item 18716 (November 1979)
and same Item 307105 (November 1989)
The relevant sections are summarized in the table below.
did. Additive type Iff RD17643 [101
8716RI1307]051 Chemical sensitizer 23
Page 6-taB right column 996 page 2 Sensitivity 11M agent
Same as above 3 Spectral sensitizer, 23-24i
'j Page 648 right column ~ 99G right ~ 9987 supersensitized
Agent Page 649 Right column 4 Brightening agent 2
Page 4 998 Right 5 Fogging prevention agent
Pages 24-25 Page 649 Right column 993 (Right ~ 1. (1
00i and stabilizer 6 Light absorber, pages 25-26, page 649, right column ~ 1
(103 left ~ i, o03 right filter dye 6
Page 50 left column UV absorber 7 Stain inhibitor Page 25 right column 650 left to right column 8
Dye image stabilizer page 25 0 Hardening agent page 26 Page 651 left column
1 (104 right ~ 1oo5 to 10 ha inder
Page 26 Same 1″ 1 (103 right ~ 1 (10
4 Right 1.1 'ijJ Plastics, lubricants Page 27 65
0 page right column ], ](106 left - 1 (106 right 12
Fabric aids, pages 26-27 Same as above 1. (10
5 left ~ 1 (106 left surfactant 13 static 2704 same as above)
1 (106 right one), (107 left inhibitor) The photographic emulsion of the present invention can be used in various color and black and white light-sensitive materials.
Can be applied. General or movie color
Negative film, slide 1 or f is for TV.
color reversal film, color paper, color positive film
1, and color reversal paper, color diffusion type photosensitive material
Typical examples include heat-developable color 1 and photosensitive materials.
can be mentioned. C plate making such as lithographic film or scanner film
X-ray film for direct or indirect medical or industrial use
film, black and white film for photography, black and white photographic paper, C0M
Ordinary microfilm, silver salt diffusion transfer type photosensitive
Photographs of the present invention are also applied to materials and print-out photosensitive materials for rice grains.
Emulsion can be applied. A color light-sensitive material to which the photographic emulsion of the present invention is applied is a support
The body has a blue-sensitive layer, a green-sensitive layer, a red-sensitive layer, or a layer sensitive to infrared light.
At least one of the silver halide emulsion layers of the corresponding layer is
The silver halide emulsion layer and non-photosensitive
There are no particular limitations on the number and order of the sexual layers. typical example and
Then, on the support, after 5 days, multiple samples with the same substantial color sensitivity but different sensitivities were placed on the support.
At least one photosensitive layer consisting of a silver halide emulsion layer of
A silver halide photographic sensitizer is equipped with an exposure chamber for photography.
It is useful for photosensitive materials with improved usability. Multilayer halogenation
In silver color photographic materials, generally a unit photosensitive layer
The arrangement is, in order from the support side, a red-sensitive layer and a green-sensitive layer.
, and a blue-sensitive layer. However, depending on the purpose
Even if the above installation side is reversed, there are also differences in the same color-sensitive layer.
It is also possible to arrange the arrangement in such a way that the color-sensitive layers are narrowed. Above, between the silver halide photosensitive layers, the top layer, and the bottom layer
A non-photosensitive layer such as various intermediate layers may be provided. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-1.13440, No. 61. −
2 (No. 1037, 61-2 (described in the specification of No. 1038)
Contains couplers, DIR compounds, etc.
Contains a color mixing inhibitor as is commonly used.
Good too. The multiple silver halide emulsion layers that make up each photosensitive layer are
, West German patent tube L12L470 or British patent tube No. 92
High sensitivity emulsion layer, low sensitivity as described in No. 3.045
A two-layer structure of emulsion layers can be preferably used. usually
are arranged in such a way that the photosensitivity decreases gradually toward the support.
It is preferable that there is a non-photosensitive layer between each halogen emulsion layer.
A sexual layer may be provided. Also, JP-A No. 57412
No. 751, No. 62-2 (No. 10350, No. 62-206)
Described in No. 541, No. 62-206543, etc.
A low-speed emulsion layer is placed on the side far from the support, and a low-speed emulsion layer is placed close to the support.
A high-sensitivity emulsion layer may be provided on the opposite side. As a specific example, from the side farthest from the support, low sensitivity blue light
Color layer (BL) / High-sensitivity blue-sensitive layer (BH) / High-sensitivity green sensitivity
Photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red
The order of photosensitive layer (RH)/low-sensitivity red-sensitive layer (RL), or
or BH/BL/GL/GH/RH/RL order, or
Installed in the order of B H/B L/GH/GL/RL/RH etc.
can do. It is also stated in Japanese Patent Publication No. 55-34932.
From the side farthest from the support, blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Tokukai also
Described in the specifications of No. 56-25738 and No. 62-63936.
Blue exposure from the side farthest from the support as shown.
Arrange in the order of sex layer/G L/RL/G H/RH
You can also do it. It is also stated in Japanese Patent Publication No. 49-15495.
The upper layer is also the silver halide emulsion layer with the highest sensitivity, and the middle layer
A silver halide emulsion layer with a lower sensitivity than that, the lower layer
A silver halide emulsion layer with lower sensitivity than the middle layer is placed.
The photosensitivity is gradually increased toward the support.
Mention may be made of an arrangement consisting of three different layers. like this
Even if it is composed of three layers with different photosensitivity,
As described in specification No. 59-202464,
Medium sensitivity from the side away from the support in the same color-sensitive layer
The layers are arranged in the following order: emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer.
They may be arranged in the order of high-speed emulsion layer, etc. To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4.101.
No. 436, JP-A-62-160448, JP-A No. 63-89
The main characters such as BL, CL, and RL described in the specification of No. 580
Donor N (C
L)'& be placed adjacent to or close to the main photosensitive layer
is preferred. It also prevents deterioration of photographic performance due to formaldehyde gas.
In order to prevent this, U.S. Pat.
Reaction with formaldehyde as described in No. 435,503
It is possible to add a compound that can be immobilized to a photosensitive material by
preferable. The photographic emulsion of the present invention is preferably used in color light-sensitive materials.
Indeed, various color couplers can be used,
A specific example of this is the aforementioned Research Disclosure (R
D) No. 17643, described in ■-C-G
Described in the patent. As a yellow coupler, for example, U.S. Patent Nos. 3 and 9
No. 33,501, No. 4,022,620, No. 4,
326°024 So, same No. 4,401. ．． No. 752, same no.
4,248,961-zu, 1)゛Publication 58. ．． 1.07
No. 39-, British Patent Tube L/125.020, No. 1
．． , 476, 760-, U.S. Patent Box 3, 973.
, 9 (i8, 4.314,023, 4,5
11. (No. i49, European Patent Box 5)], 173A
, those described in Kasa are preferred. 5-pyrasol, 1-type and
Preferred are compounds of the Phi-zoroazole type, as disclosed in the U.S. patent.
No. 4,310,61.9, No. 4.35], 897
Wing 1, R2, Europe'l;'i Permit No. 73,636, USA
Patent Box No. 3,061,432, Patent Box No. 13゜725.0G
No. 7, Reach Disclosure No. 2422
0 (1984 6 J-J l), Japanese Patent Publication No. 1986-
33552 Bow, Reach Disclosure N
o, 24230 (1984 6 JJ), JP
1986-43659 Kano, same No. 61. ,．． No. 72238,
60-357.30υ, 55-1.18f, +34
No. f160-185951, U.S. Patent Box 4,5
(10,630-'i, No. 4, 540, 654
, No. 4, 56.5.630 Lee, published on 11-1 W
Particularly preferred is 4] described in O38104795Gata et al.
. As cyan couplers, phenolic and naso [・-
U.S. Patent Box 4+ (152,2
No. 12-1 No. 4, 14 Ci, No. 391'i, No. I,
228.233 ぢ-1;3 No. 4,296,2 (No. 10, No. 2,369.929
, No. 2.801゜171, No. 2,772,162
No. 2,895,826, No. 3.112. (1
No. 02, No. 3,758,308, No. 4,343,
No. 011, No. 4,327.173-Accepted, European Patent Publication
Box 3゜329, 729, European Patent Box 1.21,365
Aman, No. 249453A, U.S. Patent Box 3.44.6
．． No. 622, No. 4,333,999, No. 4,77
5, No. 61.6, No. 4+45L559-, No. 4.
No. 427,767, No. 4,690,889, No. 4,690,889, No.
No. 4,254,212, No. 4,296,199, Special
Those described in JP-A No. 61-42658 and the like are preferred. Color L, Cap to correct unnecessary absorption of color pigments
Research Disclosure No. ] 7
643 V■-G term, U.S. Patent Box 4,163,670
, Special Publication No. 57-39413, U.S. Patent Box 4, (104
, No. 4゜1.38,258, U.S. Patent Box
1.146.368 is preferred. Also,
U.S. Patent Box 4,774. ．． Kambri described in No. 1.81
Unnecessary absorption of coloring dye due to fluorescent dye released during dyeing
A coupler that corrects the
A dye capable of forming a dye by reacting with a developing agent described in No. 0
Using a coupler with a precurly group as an H1 degroup
It is also preferable to be there. As a color coupler with moderate diffusivity,
US 1FFI Patent No. 4, 366, 237υ, UK 4J
1 No. 2,125.570, European Patent Box No. 96.570
, described in West German Patent (Publication) No. 3.23,1,533.
I really like it. Polymerized dye-forming couplers are typically
Allow box 3. ．． 151. ．． No. 820, 4,080.221
No. 4.367.288 J-1 No. 4.409.
No. 320, No. 4.576.910, British Patent No. 2,1
No. 02,173, etc. During cambling, a photographically useful lζ residue is released.
Couplers having the following properties can also be preferably used in the present invention. Development suppression
Drug-releasing DIR couplers are described in R1/76.
1.3 Patents described in paragraphs 1 to 3, JP-A-57-1
No. 51.944, No. 57-1. ．． No. 54234, 60
-18424Ft No. 63-373/16, No. 63
-37350, U.S. Pat. No. 4,248.962,
4,782.012 is preferred. Other couplers that can be used in the photosensitive material of the present invention
- as U.S. Patent Box 4. ．． 1.30,427? :
9Q This described competitive coupler, U.S. Patent Box 4,283,4
72-υ, 4.338, 393, 4.31.
Multi-equivalent couplers described in No. 0.61.8 etc., JP-A-1983
-185950, JP-A-6224525-C3, etc.
I) I R redox compound releasing coupler, I)
I coupler release force, blur, I) I I
Puller-releasing redox compound or I)
・Nox release compound, European patent box 173°3
No. 02/1, Separate rear sight described in No. 313.308A
Couplers that release colored dyes, R, D, No. 11
449, 24241, JP-A-61-201247
Bleach accelerator releasing coupler described in υ゛ et al., USA '1. f
Gantt described in it'l No. 4,553.477-j, etc.
Emitting coupler, Ro as described in JP-A-63-7.5747.
Ico dye-releasing coupler, rice +1. ]Patent No. 4. ．．
Couplers emitting fluorescent dyes as described in No. 774.181
-, etc. The color photosensitive material of the present invention includes JP-A-6.3-257
747 Kano, No. 62-272248, and JP-A-1-
1,2-henswitch azolyte as described in subparagraph 809.1.1
n-3-one, n-phytyl-P-hydroisohen
Soe I., phenol, 4-[J-ru] 3,5-dime
Thylphenol, 2-phenochotosyechnol, 2-
Various preservatives such as (4-deazolyl)benzimidazole
It is preferable to add a fungicide or a fungicide. Suitable supports that can be used in the present invention include, for example, those mentioned above.
RD, No. 17643, page 28, and the same No.
1.871.6, page 647 right column to page 648 left column
has been done. A photographic material using the photographic emulsion of the present invention has an emulsion layer.
The total thickness of all hydrophilic colloid layers on the opposite side is 28 μm or less
It is preferable, and more preferably 23ttm or less
, 20 μm or less is more preferable. Also, the membrane swelling rate TI/
□ is preferably 30 seconds or less, more preferably 20 seconds or less
. The film thickness is 25°C sum vs. temperature 55% 1 lil humidity (2 days
) means the film thickness measured at the film swelling rate T17. If, then,
Measurements can be made according to methods known in the technical field.
can. For example, in Green et al.
More 1-Graphic science and engineering
Genialing (Photogr, Sci, lEng
), Volume 19, No. 2, pages 124-129.
By using a swelling meter (swelling membrane),
T'l/2 can be measured at 30°C1 with color developer.
90% of the maximum swollen film thickness reached when treated for 3 minutes and 15 seconds
is the saturated film thickness, and the time it takes to reach 1/2 of the saturated film thickness
Defined as between. The membrane swelling rate T,/2 is due to gelatin as a binder.
Adding a hardening agent or changing the aging conditions after application
It can be adjusted by Also, the swelling rate is 1
50 to 4 (preferably 10%. Swelling rate is the maximum swollen film thickness under the above conditions)
, calculated according to the formula: (maximum swelling film thickness - film thickness)/film thickness.
Ru. The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, and No. 1
According to the normal method described in 615 left column to right column of 8716
Therefore, development processing can be performed. Also, when performing reversal processing, black and white development is usually performed.
Color development is performed. This black and white developer contains hytroxin.
dihydroxybenzenes such as ■-phenyl-3-bis
3-pyrazolidones such as laplitone or N-methyl
-Aminophenols such as p-aminophenol, etc.
Using known black and white developing agents alone or in combination
can be done. Silver halide color photographic effect using the photographic emulsion of the present invention
After desilvering, optical materials undergo water washing and/or stabilization processes.
is common. The amount of water used in the washing process is determined by
characteristics (e.g., depending on the materials used, such as couplers), uses, and
including washing water temperature, number of washing tanks (number of stages), countercurrent flow, forward flow, etc.
A wide range of settings can be made depending on the replenishment method and various other conditions.
obtain. Of these, the number of washing tanks and water volume in the multi-stage countercurrent method
The relationship is JournaI of the 5ociet
y of Motion Picture and Te
1evision Engineers Volume 64, P.
248-253 (May 1955 issue)
, can be found. According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be increased.
The residence time of water in the tank may be increased.
Due to this, grouper terriers breed, and the floating matter produced is exposed to light.
Problems such as adhesion to materials occur. Color photosensitivity of the present invention
As a solution to such problems in material processing δ,
, the calcium ionic acid described in JP-A No. 62-288゜838.
On, there is an extremely effective way to reduce magnesium ions.
It can be used effectively. Also, JP-A-57-8, 54
The isothiazolone compound and thiabendazole described in No. 2
Chlorine-based compounds such as salts, monolithium chlorinated isocyanurates, etc.
Disinfectants, other pendotriazole, etc., written by Hiroshi Horiguchi [Antibacterial
Chemistry of antifungal agents J (1986) Sankyo Publishing, Hygiene Technology
Extra notes “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
) Industrial Technology Center, Japan Antibacterial and Antifungal Society Line “Encyclopedia of Antibacterial and Antifungal Agents J
(1986) can also be used.
. The pll of washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. Washing water temperature, washing
The time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, at 15-45°C for 20 seconds to 10 minutes, preferably
The temperature is selected to be in the range of 30 seconds to 5 minutes at 25 to 40"C.Furthermore, the photosensitive material of the present invention can be stabilized directly instead of washing with water.
Can be treated with liquid. Such stabilization
In terms of science, JP-A-57-8543 and JP-A-58-14
No. 834 and the known method described in No. 60-220345
You can use all of them. In addition, when a stabilization treatment is performed following the water washing treatment,
An example of this is 4. color sensitivity for photography. (r'+
Porumari:,/bath used as the final bath of
It can be done. Examples will be described below. Example 1 A hexagonal flat plate with a halogen structure with an average iodide water content of 8 mol% of N.
An emulsion containing tabular silver chloroiodobromide grains was prepared. grains of rice
Child: TIA contains 2% silver iodobromide containing 2% silver iodide.
The first coating layer contains 5 mol% silver chloride and 10% silver iodide.
Silver iodochlorobromide containing mol%, average volume-loaded sphere equivalent diameter
The value is 0.75μ, the ratio of particle diameter to thickness (aspect ratio)
is 8.0. The distribution of silver iodide and silver chloride amounts among grains is
The coefficients of variation were 6.5% and 5.0%, respectively. particle
The Zeiss coefficient of variation was 14%. This emulsion is used as a base milk.
It was named agent (IA, ). ]-kg of emulsion CIA) and distilled water]! Mix 60
1% silver chloride per mole of silver in the base grains.
While stirring to make epitaxial growth at the top.
0.5% potassium iodide aqueous solution 1 (10cc for 3 minutes)
After adding the silver nitrate aqueous solution and sodium chloride
Added by double jet. After epitaxial growth, the base grains are further grown in a second layer.
Silver nitrate aqueous solution and potassium bromide to grow the coating layer.
An aqueous solution of 25% silver bromide per mole of silver in the base grains was precipitated.
It was added using the double jet method so that it would coat the liquid. This addition
Prior to this, add 0.5% potassium iodide aqueous solution 1 (10 cc
was added over 1 minute. Furthermore, a third coating layer containing 10 mol% of silver iodide is applied to the base grains.
silver nitrate aqueous solution and bromide to grow 5% per mole of silver.
Double jet a mixed solution of potassium and potassium iodide.
Added with. From electron microscopy observation of these emulsion grains, we found that the
It was confirmed that dislocations were concentrated in the corners, so
It was named rearrangement emulsion (II-A). In the process of preparing emulsion (U-A), silver chloride is added to the top of the emulsion.
Excluding pitaxial growth process and 2% potassium iodide
Create an emulsion by adding um aqueous solution 2 (10 cc in 1 minute)
did. Electron microscopic observation of emulsion grains reveals that dislocations are present in the grains.
We confirmed that it has been introduced throughout the surrounding area.
, non-concentrated type 1ii: emulsion (DI-A) and name I-J
Got it. Preparation of emulsion (II-A) - [In the culm, silver chloride emulsion
Excluding pitaxial growth and addition of potassium iodide aqueous solution
An emulsion was prepared. An observation of this emulsion grain using an electron microscope
Since we have confirmed that there are no dislocations in the particles of Haton,
, dislocation-free emulsion (IV-A) Hitoshi Dona] 63 Noko. Emulsion (11-Δ), (In-A), (IV
In the same process as △), take 1 kg of emulsion (IΔ) and distill it.
When mixed with 1N of water, silver per mole of base particles
The oxidizing agent (compound 1-2 in Table A) was added to the
and emulsion (II-8). Named (III-F3) and (IV-B)
. Similarly, an emulsion containing 5 x 10-'' moles of hydrogen peroxide was prepared.
7L agent (+[-C), (III C), respectively.
), (1\I C) and the name I・1(). Furthermore, the same
Dear 7. The oxidizing agent (compound 1-2 in Table A) was added to 5X10-
'While growing the second coating layer after adding molar
As a reduction sensitizer in 1. − Ascorbic acid is added to the base particles.
Each emulsion containing 2XlO−' mol per mol of silver
, Emulsion (II-1)). They were named (II-D) and (IV-D). On the other hand, hexagonal, square, and triangular shapes with an average iodine content of 8 mol%
Examining amorphous thick silver chloroiodobromide grains in which irregularly shaped grains are mixed.
Manufactured. Volume load sphere equivalent diameter is 0.75μ and mo-uniform aspect
The pitch ratio was 1.8. This emulsion is used as a base emulsion (I B
) and the name (1.
11-A) Similar epitaxial growth and second coating layer
Growth and addition of oxidizing agent to silver and reduction sensitization
(V-Δ), (V-B). (VC) and (■-1)) were prepared. Each emulsion was divided into two parts, and one emulsion was desalted (30°(:
Add sensitizing dye ■ shown in Table 8 below and compound F-3.
Etanora, redispersed, lithium sulfate, thione
Add potassium anate and chloroauric acid to 60°C160
Each was optimally chemically amplified for 1 y. Each emulsion is converted into
Immediately before sensitization, an oxidizing agent (compounds 1.-16 in Table A)
) was added at 3 x 1.0-' moles per mole of silver. these
The emulsion was used in Example 2. The other emulsion was desalted and redispersed, and then 1-lium thiosulfate was added.
, potassium thiocyanate, and chloroauric acid at 60°C.
Optimally chemically sensitized for 160 minutes, and
It was made into an emulsion for layer coating. Example 2 Triacetylcellulose film with undercoat layer
Apply the emulsion and protective layer to the support in the coating amounts shown in Table 1.
was applied. Table 1 (1) Emulsion layer Emulsion: Emulsion shown in Table 2 (silver 1.7X10-2 mol/m2) Coupler (1,5XIO-3 mol/m2)
Liclesyl phosphate (1,IOg/m2) Gelatin (2,30g/m2)
(2) Protective layer・2. 4-dichlorotriazine-6-hydroxy-
3-triazine sodium salt (0,08g/m2) Gelatin (1,80g/m2
) Before exposure, each sample was folded using a folding tester, and then
After exposure for cytometry, the next color development process is performed.
It was. The concentration of the treated sample was measured using a green filter. G The results of the photographic performance obtained are shown in Table 2. The development process used here was carried out at 38°C under the following conditions.
. 1. Color development... 2 minutes 45 seconds 2. Drifting
White... 6 minutes 30 seconds 3, wash with water...
・・・ 3 minutes 15 seconds 4, established ・・・ 6 minutes 3
0 seconds 5, wash with water 3 minutes 15 seconds 6, low
Setting... 3 minutes 15 seconds Processing set used for each process
The composition is as follows. Color developer 21heliolotriacetate sodium 1.4g sulphurous
Sodium acid 4.0g Sodium carbonate
30.0 g potassium bromide
1.4g hydroxylamine
Sulfate 2.4g4-(N-ethyl-N-
Add 4.5g of β-hydroxyethylamino)-2-methyl-aniline sulfate water.
Te 1! Bleach solution ammonium bromide 160.0 g
Ammonia water (28%) 25.0m
ff1 Ethylenediamine-tetraacetic acid sodium salt 130g glacial acetic acid
Add 14 ml water
12 fixer. Sodium tetrapolyphosphate 2.0g sulfite
Sodium 4.0g Anthiosulfate
Monium (70%) 175.0m2 Sodium bisulfite
Add thorium 4.6g water
II! . Stabilizing liquid formalin 8.0ml water
Plus 1! Exposure is 1/
A normal wedge exposure was performed for 1 (10 seconds). A color temperature of 48 (10' K) was used as the light source using a filter.
Use a yellow filter adjusted to
Using. Sensitivity is 0.2 point in optical density from fog
compared with. Folding] - The result of the strike is haze and desensitization due to folding.
compared. The fog is noticeably high, or the desensitization range is large.
Let N (f be the sample that cannot withstand practical use)
child. Example 3 Undercoated cellulose triacetate film 11 support layer -
Then, apply multilayer coating A) with each layer having the composition shown below to form a multilayer coating.
Sample which is a color photosensitive material], OI was prepared. (Photosensitive layer composition) The numbers corresponding to each component are expressed in g/m'' units.
Indicates the coating amount, and for silver halide, it is the coating amount in terms of silver.
Indicate quantity. However, regarding aggravating pigment,
The amount of coating per mole of silver germide is expressed in terms of moles. (Sample 101) 1st layer (anti-halation layer) Black two-layer solid silver granite 0818
Latin 1.40 2nd layer (
Intermediate layer) 2.5-GC pentadecyl hydride 1 coquinone 0.1SE
X-], 0.0
701”:X3
0.020Eχ-122,OX 10-” U-10,060 U-20,080 U-30,1,0 HBS-1,0,10 HBS-20,020 Seratin 1.04 3rd layer
(First red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B
Root 0.25 sensitizing dye 1
'6.9 Xl0-'sensitized color
Elementary II 1.8 X 1.0-
'Sensitizing dye III 3.1.
X], O-'E X-20,34 E
60 gelatin 0.87th
4 layers (second red-sensitive emulsion layer) Emulsion G Silver 1. (10 sensitization
Dye 1 5. I Xl0-5 increase
Sensitive dye II 1.4 Xl0-
5 Sensitizing dye III 2.3X
l0-'E X -20,40 8X -30,050 E
(Third red-sensitive emulsion layer) Emulsion D Silver 1.60 sensitized color
Prime 1 5.4 Xl0-5 sensitized
Dye II' 1.4X10-
5 Sensitizing Dye III 2.4X
l0-'EX-2,0,097 EX-30,010 EX-,40,080 HB S-10,22 HBS-20,10 Gelatin 1.63 6th layer (
Intermediate layer) EX -50,040 HBS-10,020 Gelatin 0.80 7th layer (
1st green-sensitive emulsion layer) Emulsion A Silver 0.15 Emulsion B
0.15 sensitizing dye IV
3.0X10-5 sensitizing dye V
1. OXl0-'sensitizing dye
VI 3.8 Xl0-'EX
-10,021 EX-60゜26 EX -70,030 EX -80,025 HBS-10,10 HB S -30,010 Gelatin 0,63 8th layer (
Second green-sensitive emulsion layer) Emulsion C silver 0.45 Sensitizing dye IV 2.0 Xl0
-5 Sensitizing dye V7.0XIO-' Sensitizing dye Vl 2.6X]O-
'EX-60,094 EX-70,026 EX-80,018 HBS-10,16 IB s-38,0xlO-' Gelatin 0.50 9th layer (
3rd green-sensitive emulsion layer) Emulsion P, silver 1.20 enrichment
Dye IV 3.5 Xl0-5
Sensitizing dye V8. OXl0-
5 Sensitizing dye Vl 3.0X10
-'Eχ-I O,02
SEX-1,1,0,10 EX-130,015 HB S-10,25 HBS-20,10 Gelatin 1.54 10th layer
(Yellow filter layer) Yellow colloidal silver Silver 0.050E
X-50,080 HB S -10,030 Gelatin 0.95 11th layer
(First blue-sensitive emulsion layer) Emulsion A Silver 0.080 emulsion
B Silver 0.070 emulsion F
Silver 0.070 sensitizing dye
■ 3.5X10-'Eχ-80
,042 EX-90,72 HB S-10,28 Gelatin 1.10 12th layer
(Second blue emulsion layer) Emulsion G Silver 0145 sensitized color
Basic ■ 2. I Xl0-'E
X-90,15 P
Layer (Third blue-sensitive emulsion layer) For emulsion-I Silver
0.77 sensitizing dye ■ 2.2X
lO'1roX-90,20 1-I B S -1,0,070 Seratin 0.69 No. 14
Layer (first protective layer) Emulsion I Silver 0.20TJ-
40,11 1 no 50.17 II B S -] 5. O
X 10-” powder 1
, (10 15th layer (second protective layer) + (-10,,10 B-1, (diameter 1.7 um) 5.0
Xl, 0-”I32 (diameter 1.7 μm)
0.1Of3-. 3
0.10S -1,0,20 Gelatin 1.20 Furthermore, total
The layer has storage properties, processability, pressure resistance, anti-mold/bacterial properties, and anti-static properties.
In order to improve the adhesion and coating properties, W-1, W-2,
AL-3, B-4, B-5, F-1, F-2, F-3,
F-, 1, F-5, F-6, F-7, F-8, F-9,
F 10, F-11, F-12, F-13 and iron salt,
Contains lead salts, gold salts, platinum salts, iridium salts, and rhodium salts
has been done. Next, the contents of emulsion A-1 will be shown. Also,
The structural formula of the compound is shown in Table 8 below. Replaced with emulsion, (11-A) to (11-D). Six types of emulsions (III-A) and (IV-A) are used in the fifth layer.
I prepared a mixer that I put in. According to Example 2
When sensitometry was performed, (IIB). Three types of emulsions (II-C) and (ll-1) were used.
The photosensitive material has high sensitivity, and the results of the bending test 1-
It was good. Example 4 As described in the examples of U.S. Pat. No. 4,668,61.4
The final size is determined according to the recipe of monodisperse octahedral double structure particles
1. u (emulsion V), 1. ．． 5tt
(Emulsion ■) and 1.671 (Emulsion Vll) were prepared.
Ta. In the manufacturing process of Gorera emulsion, 30 mol% of iodine
After preparing the silver bromide core particles, forming the silver bromide shell
Stop the growth midway through the process and add an oxidizing agent (1-2 in Table A).
After that, a process for introducing vertex dislocations was performed in the same manner as in Example 1.
Add L,-ascorbic acid, and then add the remaining
A second silver bromide shell was added. These emulsion grains and
The coefficient of variation of -is is 18% for emulsion ■ and 15% for emulsion ■.
, Emulsion ■ was also 15%. These octahedral emulsions were chemically sensitized according to the method of Example 1.
After that, the emulsion of the 5th layer is changed to emulsion ■, and the emulsion of the 9th layer is changed to
In addition, the emulsion in the 12th layer was replaced with emulsion Vll.
A multilayer color photosensitive material shown below was prepared. Example
When center I measurement was performed according to 2, the present invention was found.
The light-sensitive materials containing emulsions V to ■ have high sensitivity and
The results of the bending test were also good, and the unexposed film was
Aging for one week at 50°C and 30% relative humidity.
It is new that the amount of increase in fog during the test has been reduced.
It was discovered recently. (Composition of photosensitive layer) The coating amount is g of silver for silver halide and colloidal silver.
/m2 and couplers, additives and gelatin.
For tin, the amount expressed in g/m2, and for sensitizing dyes
is the mole per mole of silver halide in the same layer.
Shown in numbers. 1st layer (antihalation layer) Black colloidal silver...0.2ze
Latin...1,3UV-1
...0.05 UV-2...0.05 UV-3...0.10 UV-4...0.10 0i1-1 ...0.1 (1
0i1-2 ...0.10th
2nd layer (middle layer) Gelatin...1.0 3rd layer
Layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (AgT 7.1 mol%, octahedral multiple structure
Particle, volume equivalent spherical diameter 0.4 μm, coefficient of variation of spherical equivalent diameter
15%) Coated silver amount...1.0 gelatin
...2,03-1
...2.8 Xl0-'S-2...2.0X
10-' S-3... 0xl0-5 Cp-1...0.40 Cp-2...0.040 Cp-3...0.020 Cp-4...0. (1020 0il-1...0.15 0i1-2
...0.15 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (AgT7.7 mol%, octahedral multi-structure grains
volume equivalent spherical diameter 0.8 μm, coefficient of variation of spherical equivalent diameter 1
0%) Coated silver amount...1.20 gelatin
...0.83-1
...2.0X10-'S-2...1.5X
IO-'S-3...8.0X10-' CP-1...0.30 Cp-2...0.03 CP-3...0.03 Cp-4...0. (102 0i1-1 ...0.12
0il-2...0.12 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 8 mol%, octahedral multi-structure grains
, volume equivalent spherical diameter 1.1 μm, coefficient of variation of spherical equivalent diameter 13
%) Coated silver amount...1.0 gelatin
...1.5O3-1...1.5X10
-'S-2...1.5X10-' S-3...8. OX]O-'''cp-i...0.10
Cp-2...0.10 0i1-1...0.05
0i1-2...0.05
6th layer (middle layer) Gelatin...0.70C
pd-11...0.03 0i1-1...0.05
7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (8gI 7 mol%, octahedral multi-structure grains
, volume equivalent spherical diameter 0.4 μm, coefficient of variation of spherical equivalent diameter 15
%) Coated silver amount...1.10 Seratin
...2.5O3-4...2.4X1
0-'S-5...2.4X10-' S-[5... 1.2 X 1O-4 S-7...5.0 xlo Cp -5...0. ■5 Cp-6...O, 1,0 (]p-7...0.0:+ Cp 8
...0.020i1-1
...0.3 (10 i I-2...
・0.30 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (static I7.3 mol%, octahedral multiple (I11
Heavy particle, volume equivalent spherical diameter 0.771 m, equivalent to fJi
Coefficient of variation of diameter 9%)/P cloth silver armor...j, 10 sera
Chin...0.8O3-4
...2.0XIO-'S-5...1.9X1.0=S-6...], 1. Xl0-'3-7...4.0XIO'
Cρ 5 ...(1,1(
10ρ-6...0.07 (1 cp -7...0.030 (]5 Cp-8...0.025 0i ]-1...0.20 0i1-2 ・
...0.20 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (Ag17.5 mol%, thick plate aspect ratio
2. Volume equivalent sphere diameter 1.5/1m, coefficient of variation of sphere equivalent diameter
14%) Coated silver amount...1.20 gelatin
...1.8O8-4...1.3X
1.0-'S-5...1.3X10-'S-6...9.0X10-'S-7...3.0X1.0-' Cp-6...0.20 0p -7...0.03 0i1-1...0.2(
10i1-2...0.0
5 10th layer (yellow filter layer) Gelatin...1.2 Yellow layer
Lloyd silver...0. (18Cp
d-12...0.1 011 1...
・0.3 11th layer (first blue-sensitive emulsion layer) σ, bromide 'M emulsion (A8I (i, 5 mol%, octahedral multiple
Structural particles, volume equivalent spherical diameter 0.4 μm, variation in spherical equivalent diameter
Coefficient: 9%) Coated silver amount...0.20 Odorized emulsion (
8l: 17%, hehedral polyflj, )'1'l j
'H'i particle, volume equivalent spherical diameter 0.871m, spherical equivalent diameter
change J coefficient 12%) coating'jf3. Purchase ・0.45
Seratin...1.753
-7...], ]OX],
0-'S-8...2.0XI
O”0.4] ...0.
/15Cp-10...0.50 0i1-1...0.2(
10i1-2...0.1
0 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (target, I'9.7 mol%, thick plate Asparagus 1
- J:t; 2, volume equivalent spherical diameter], 6 pm,
f3 [coefficient of variation of equivalent diameter 12%] Coated silver amount...1
．． 10 Gelatin...1.
20S-7...1. OXl, 0-' 5--8...complete, OXl, 0-' Cp-9...0,25 0il-1...0.060 0i1-2 ・
...0.030 13th layer (first protective layer) Fine grain silver iodobromide (average particle diameter 0.08 μm, static 2 mol)
%) ...0.40 gelatin
...1.30UV-1...
・0.05 UV-2...0.05 t, J V-3...0.10 1ノ■-4...0.10 tJV-5...0.03 0jl 1... 0.10i
1-2...0.1 14th
Layer (second protective layer) Gelatin...0.50 world
Surfactant (W-1,1) =-0,1,
0 polymethylmethacrylate-1-particles...0.2
Scratching agent (B~11')...0
．． 03H-1...0.4'' In addition to the above components, coating aid W-12. Dispersion aid W-
1,3, Hardening agent H-11,1-T-] 2, Formalin
Scavenger-Cpd-13, Cpd-14, preservative
In addition to Cpd-15 and Cpd-16, the stabilizer Cpd
-17, with antifoggant Cpd-18°Cpd-19
added. Chemical structure of the compounds used to create these samples
The formula or name is shown in Table 0 below. Table A (11) CHSSO2Na (1-2) C2H5So□5Na (13) C,I-175O2SK (1-4
) C4H9SO□S I-1(1-5) C6H,,
+502SNa(16) Ca H+7SOz 5Na
'CH3(CHz)3 CHCHzSOzS-NH
4zHs (18) CIaHz+5C)45Na(1-9)C
l2H2SSO25Na(1-10) C,6H,,5
O2SNa(112) t-C4H95O2SNa(1
-1,3) CH30CH2CH2SO2S-Na(1
15) CH2=CHCH25O, SNa/ -'-
-\ (1, -29) NSSO2(CH,,) 2 So 2 SK(+
-3(1) N a S S Oz (C112)4S 02S N
aN a S S 02 (CH2) 4S (CH2)
4S 02S Na SO25Na (], -33) -, -, -(-CH-CH2-)-, -(-CH-C)
+2-→-W ”-S 02 S Na x:y=1/1 (molar ratio) (2-],) C2H5So□ S -, -CH. (22) C0HI7SO□ S CH□ CH□
(1-5) C2H5SO□ S CJ(,,Cf
I2CN(2-7) CI
(3□ C, H7SO□ 5CHCH2CN (2-1,0) (2-1,3) C2H5SO□S CH2CH2CH2CH20Hl,
O6 CI(,SSO□ (CHz)a SO25CI-
(3CH35S02 (CH2)z so□S CI-
13CH25SO7C2H5 x:y=2/1 (molar ratio) C2HsSO□5CII zcHzsO□CH□CH□
5SO2C2115C2H5So□ 5sso□ C2
H3(II)C3H, So□ 5SSOz C3H7
(II) Section B Table 1] X-3 l1 EX-4 11+1 E
CI+31X-10 ci+. IEX-], 1 [;1 EX-12 C2II S C2H5C2H5
0SO30 EX-13 I U-3 J-4 χ: y = 70:30 (4%) J-5 HBS-1) Licrisyl Phosphe-1/HBS-2 Di-
n-Butyl phthalate B5-3 Sensitizing dye I Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye V Sensitizing dye■ Sensitizing dye■ (CHz)4Soρ (CH2) asO311-
N(C21(5) 3)IH CH2=CHSOz CHz C0NHCHzCH
2==CH-SO□-CHz C0NHCH2B-1 CH, ni113 ---(-C11?, -C--to]--

[-ClI2
C-→-,-x/y, 10/90COOII
C (10C113CL
CtL+ −−−(−CII□−C−−−−)−1□□(C11□
-C---)-"x/y40/60COOII
C(10Ct(3Cll:+
CI(3 (Cfh) 3sio (-5i-0→-rq-(
-S i -(10-4-6-- Si (C113
)3■3-4 −+ C112-CH→−★−−−←CH, CII→−
9-x/y=70/30COO14a ■Par-4 ]21 1'-6 F-10 F-11 H Table C V-1 I V-2 C] V-3 V-4 V-5 oil-1 Tricresyl phosphate oiI-2 Dibutyl phthalate p-2 P-3 p-4 Cp-5 I Cp-6 Cp-7 I Cp -8 p-9 White Cp -1,0 I Cp d-1,1 C11 ■ 29 Cp d -1,2 n+1! 1 Cp d-1,4 (I Na03S C11COO(Jlz(CF2CF2)
311C) 12cOOcIl□(CF2CF2) :+
i11, 3 0 W-12 NaOzS CtlCOOCeH+7CHzCOOC
oll+7 pd-15 pd-17 H Cp d-1,9 (CIlz) 4SOz-Cztls (CI+2) SSOz-(Cllz) zsOJa(
(:Hz)3S03- CHzCHzCHS
OJa CI+3 S-8

Claims (12)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the emulsion layer are mainly composed of (111) planes. , dislocations are concentrated near the apex of the particle,
A silver halide photographic material characterized in that an oxidizing agent for silver is added during the production process of the silver halide emulsion. (2) The oxidizing agent for silver has the formula (I), (II), or (
The silver halide photographic material according to claim (1), which contains at least one compound selected from the compounds represented by III). (I) R-SO_2S-M (II) R-SO_2S-R^1 (III) RSO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different, It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. Compounds of formulas (I) to (III) are (I) to (III).
It may also be a polymer containing a divalent group derived from the structure shown in III) as a repeating unit. Further, when possible, R, R^1, R^2, and L may be bonded to each other to form a ring. (3) A silver halide photographic light-sensitive material, wherein the silver halide emulsion according to claim (1) is reduction sensitized in the step of forming silver halide grains. (4) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the emulsion layer are mainly composed of (111) planes. , and 60 of the total projected area of the silver halide grains.
% or more is occupied by tabular grains with an aspect ratio of 3 or more,
A silver halide photographic light-sensitive material, wherein dislocations are concentrated near the apexes of the grains, and an oxidizing agent for silver is added during the production process of the silver halide emulsion. (5) The oxidizing agent for silver has the formula (I), (II), or (
The silver halide photographic material according to claim (4), which contains at least one compound selected from the compounds represented by III). (I) R-SO_2S-M (II) R-SO_2S-R^1 (III) RSO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different, It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. Compounds of formulas (I) to (III) are (I) to (III).
It may also be a polymer containing a divalent group derived from the structure shown in III) as a repeating unit. Further, when possible, R, R^1, R^2, and L may be bonded to each other to form a ring. (6) A silver halide photographic light-sensitive material, wherein the silver halide emulsion according to claim (4) is reduction sensitized in the step of forming silver halide grains. (7) A silver halide photograph characterized in that the vicinity of the surface of the silver halide grains contained in the silver halide emulsion of claim (4) is made of silver halide containing 5 mol % or more of silver iodide. photosensitive material. (8) A silver halide photographic light-sensitive material, wherein the silver halide emulsion according to claim (7) is reduction sensitized in the step of grain formation. (9) In a silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on a support, silver halide grains contained in the emulsion layer are normally composed mainly of (111) planes. 1. A silver halide photographic material comprising crystalline grains in which dislocations are concentrated near the vertices of the grains, and in which an oxidizing agent for silver is added during the manufacturing process of the silver halide emulsion. (10) The silver halide photographic material according to claim (9), wherein the oxidizing agent for silver is selected from at least one compound represented by formula (I), (II), or (III). (I) R-SO_2S-M (II) R-SO_2S-R^1 (III) RSO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different, It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. Compounds of formulas (I) to (III) are (I) to (III).
It may also be a polymer containing a divalent group derived from the structure shown in III) as a repeating unit. Further, when possible, R, R^1, R^2, and L may be bonded to each other to form a ring. (11) A silver halide photographic material, wherein the silver halide grains contained in the silver halide emulsion of claim (9) have a monodispersity in size distribution with a coefficient of variation of 25% or less. (12) A silver halide photographic light-sensitive material, wherein the silver halide emulsion according to claim (9) is reduction sensitized in the step of forming silver halide grains.