JP2003280133A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in sensitivity and graininess with respect to a photographic sensitive material including silver halide emulsion layers comprising silver halide tabular grains having ≥3.5 μm equivalent circular diameter. <P>SOLUTION: The silver halide color photographic sensitive material has on a support a unit blue-sensitive silver halide emulsion layer, a unit green- sensitive silver halide emulsion layer and a unit red-sensitive silver halide emulsion layer each consisting of two or more color-sensitive layers different from each other in sensitivity, wherein grains which occupy ≥50% of the total projected area of all silver halide grains in at least one of the emulsion layers included in each unit color-sensitive layer in the sensitive material are tabular silver halide grains having (111) faces as principal planes and ≥3.5 μm equivalent circular diameter, and the water swelling rate T of the sensitive material is ≥1/45 [sec<SP>-1</SP>]. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention is excellent in sensitivity and granularity.
The present invention relates to a photographic photosensitive material. [0002] 2. Description of the Related Art One or more photosensitive layers are contained on a support.
Are known in the art as photosensitive materials.
It is. In the case of a color photographic light-sensitive material, it is blue during exposure.
Selective exposure to each wavelength range of green and red, during development processing
Each layer is colored yellow, magenta and cyan.
Placed on top. Each layer contains silver halide grains
Silver halide emulsions and yellow, magenta, and shear
It is composed of couplers that develop colors. Halogen as an element for recording by exposure to light
For silver halide grains, efforts to increase sensitivity to light
Power has been made. Each wavelength range of blue, green and red
As a method for selectively absorbing silver on the surface of silver halide grains
Methods for adsorbing spectral sensitizing dyes are widely known. Feeling
In order to increase the degree, the silver halide grains are tabular and the ratio table
Increasing the area and increasing the amount of sensitizing dye adsorption
In recent years, tabular grains have been further reduced in thickness.
(Ultrathin tabular grains) have been used. However, when ultrathin tabular grains are used,
Reported a significant drop in sensitivity due to large particle reflections
(Research Disclosure, 25330, 1
985, A.E.Bohan, G.L.House, J.Imag.Sci.38, 32 (1
994)). Therefore, such ultrathin tabular grains are colored.
-Sensitivity decreases when used in photosensitive materials, and other photos
It is anticipated that the characteristics will be degraded in JP-A-11-316433
Has been described. Photosensitive materials can be used for development processing after exposure.
Chemical treatment is applied. In the case of color photosensitive materials, development
-Bleaching-fixing step (including water washing step) is performed. developing
The rate of swelling of the gelatin-containing layer, and the chemical species
Influenced by diffusion rate. In general, color photosensitive materials are hot.
Since it is developed at 38 ° C for color negatives,
Additives often referred to are introduced. In addition, hardener
Water resistance, heat resistance and wet abrasion resistance of photosensitive materials by introduction
It is known that the property is also improved. On the other hand, the photosensitive material
The optical density, or contrast, is affected by the degree of hardening.
Therefore, there is an optimal dura degree. JP-A-11-316433
Then, the water swelling ratio of one layer of the silver halide emulsion layer is changed to the water of the other layer.
Increasing the swelling rate improves the photographic performance.
Yes. [0006] The object of the present invention is to provide a circular phase.
HA containing silver halide tabular grains having a diameter of 3.5 μm or more
In a photographic light-sensitive material containing a silver halide emulsion layer,
Providing photographic materials with excellent sensitivity and graininess
The [0007] The object of the present invention is as follows.
Achieved by dan. (1) Two or more color-sensitive layers having different sensitivities on the support.
Unit blue-sensitive silver halide emulsion layer, unit green
Sensitive silver halide emulsion layer and unit red sensitive halogenation
A silver halide color light-sensitive material having a silver emulsion layer.
The emulsion layer contained in each unit photosensitivity in the photosensitive material
The projected area of all silver halide grains in at least one layer
Particles occupying 50% or more have the (111) plane as the main plane
Tabular silver halide grains having an equivalent circle diameter of 3.5 μm or more
The photosensitive material has a water swelling speed T of 1
/ 45 [sec^-1] Halogenation characterized by the above
Silver color photographic light-sensitive material. (2) For each unit photosensitivity in the photosensitive material.
Total halogenation in at least one of the included emulsion layers
Particles occupying 50% or more of the projected area of silver particles are (11
1) A plane having a circle-equivalent diameter of 4.0 μm or more with the plane as the main plane
It is composed of tabular silver halide grains
The silver halide color photographic photosensitive material according to (1) above
material. (3) The water swelling speed is 1/40 [se
c^-1Or above (1) or
The silver halide photographic light-sensitive material as described in (2). (4) At least the emulsion layer in the light-sensitive material
50% or more of the projected area of all silver halide grains in one layer
The equivalent particle diameter with the particles occupying the top having the (111) plane as the main plane
3.5 μm or more, average silver iodide content of 5 mol% or more
It is composed of tabular silver halide grains
Any one of (1) to (3), which is characterized
The silver halide color photographic light-sensitive material listed. (5) According to the tabular silver halide grains described above
Unit color sensitivity of two or more layers with different emulsion layers
In the most disperse emulsion layer
Any one of (1) to (4) above
Silver halide color photographic light-sensitive material. (6) According to the tabular silver halide grains described above
The emulsion layer composed of
Being at the farthest position from the support in the emulsion layer
In any one of the above (1) to (5), characterized in that
The silver halide photographic light-sensitive material described. (7) According to the tabular silver halide grains described above
The thickness of the emulsion layer that is composed when dried is 3.0 μm or less.
(C) the above described (1) to (6)
Silverogen color photographic light-sensitive material. (8) By the tabular silver halide grains
The amount of silver contained in the constituted emulsion layer is 0. 0 in terms of Ag.
1g / m²2.0 g / m²It is characterized by
Silver halide photographic sensitivity as described in (1) or (7) above
Light material. (9) By the tabular silver halide grains
Adjacent to the constituted emulsion layer, the grain thickness is 0.2 μm or less.
Below, tabular halogenation with an average silver iodide content of 3 mol% or less
Silver particles 0.1g / m in terms of Ag²2.0 g / m²Less than
(1) characterized in that a lower emulsion layer is disposed
To a silver halide column according to any one of (8) to (8)
-Photosensitive materials. [0016] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.
explain. First, the silver halide emulsion in the present invention is described.
I will explain. Composition of silver halide grains in the present invention
Is preferably silver iodobromide or silver iodochlorobromide. Silver halide grains
The form of the child is preferably a tabular grain.
In the present invention, there are two tabular grains (hereinafter referred to as tabular grains).
Halogenation with opposite parallel (111) major planes
Say silver particles. The tabular grain of the present invention has one twin plane.
Has two or more parallel twin planes. The twin plane is (11
1) The ions of all lattice points are in mirror image relation on both sides of the surface.
This is the (111) plane. This tabular grain
Is a triangle when the particle is viewed from a direction perpendicular to the principal plane.
Shape, hexagonal shape or round shape with round shape.
The main planes are parallel to each other. flat
The equivalent circle diameter and thickness of the plate particles are measured by the replica method.
Take an over-electron micrograph to measure the projected area of each particle, etc.
Find the diameter (equivalent circle diameter) and thickness of a circle with a large area
The In this case, the thickness is the length of the shadow of the replica
Calculate from The emulsions that can be used in the light-sensitive material of the present invention
Explanation of one (hereinafter also referred to as “first emulsion”)
To do. The first emulsion that can be used in the present invention has an equivalent circle diameter.
Tabular grains of 3.5 μm or more are projected from all silver halide grains
Occupies 50% or more of the area. Equivalent circle diameter of 3.5μm or more
The proportion of tabular grains in the total projected area is preferably 50% or more.
More preferably, 70% or more is more preferable. The equivalent circle diameter is 3.5 μm or more and 20.0 μm.
The following is preferable, and 4.0 μm or more and 10.0 μm or less is preferable.
Further preferred. Sphere equivalent diameter is 1.0μm to 5.0μm
Is preferably 1.2 μm or more and 4 μm or less.
Good. Spherical equivalent diameter is the volume equal to the volume of each particle
The diameter of the sphere with The aspect ratio is 8 or more
Preferably 200 or less, more preferably 10 or more and 100 or less
preferable. Aspect ratio is the equivalent circle diameter of a particle.
The value divided by the thickness. The emulsion of the present invention is preferably monodispersed.
Yes. Variation coefficient of equivalent spherical diameter of all silver halide grains of the present invention
Is 30% or less, preferably 25% or less. Also flat
In the case of plate-like particles, the coefficient of variation in equivalent circle diameter is also important.
The variation coefficient of equivalent circle diameter of all silver halide grains of the invention is 30
% Or less, more preferably 25% or less.
It is below. The variation coefficient of the thickness of the tabular grains is 30
% Or less is preferable, and 25% or less is more preferable. Changer
The number is the standard deviation of the equivalent diameter distribution of individual silver halide grains.
The difference divided by the average equivalent diameter or individual halogen
Divide the standard deviation of the thickness distribution of tabular silver halide grains by the average thickness.
It is a value. In the emulsion which can be used in the light-sensitive material of the present invention,
(111) plane occupying 50% or more of the total projected area
Of a tabular grain having a major equivalent plane with an equivalent circle diameter of 3.5 μm or more
Average silver iodide content (the ratio of silver iodide to the total silver content in the grain)
Is preferably 5 mol% or more. In the present invention
In this case, the silver iodide content in the silver halide grains is
0.5 mol% or more and less than the solid solution limit with respect to the total amount of silver in the grain
However, 5 mol% or more is preferable. The silver chloride content is
0 mol% or more and 10 mol% or less with respect to the total silver amount in the grain
preferable. Silver halide flat plate contained in the emulsion of the present invention
The grains preferably have different silver iodide contents.
A part and a shell surrounding the core part.
It may have a so-called core / shell structure. Shell part is
The side of the tabular grain in the core may be surrounded
May surround only the main plane,
Also good. The number of shells is one or more,
Also good. The silver halide grains in the present invention are the grains
The area from the outer periphery of the child projection part is within 20%, preferably 1
Dislocation lines may exist in a portion within 0%. The dislocation line is
It may exist along the outer periphery in the vicinity of the outer periphery,
It may be localized near the portion. Near the corner is the particle
The point at x% from the center of the straight line connecting the center and each vertex
When a perpendicular line is drawn on the edge that makes each vertex,
It is a three-dimensional part surrounded by the sides. This x
The value is preferably 50 or more and less than 100, more preferably
75 or more and less than 100. One dislocation line exists per particle
An average of 10 or more is preferable. More preferably one particle
Average 20 or more. In the present invention, the silver halide grains are tabular.
Protruding part (hereinafter referred to as epitaxial) outside the particle
May exist. Junction to epitaxial tabular grains
There are few corners, edges, and main planes of tabular grains.
At least a part may be sufficient, and it may be spread over several places.
Yes. The epitaxial composition is AgBr, AgCl, Ag.
BrCl, AgBrClI, AgBrI, AgI, Ag
SCN and the like are preferable. In addition, the
“Dopants” as described in US Pat. No. 8-69069
(Metal complex) "may be introduced. The above-mentioned first emulsion is the light-sensitive material of the present invention.
Can be used in any emulsion layer.
The photosensitive material of the invention is composed of two or more emulsion layers having different sensitivities.
Unit blue sensitive emulsion layer, unit green sensitive emulsion layer, and unit
When composed of red sensitive emulsion layers, each of blue, green and red
Each of the emulsion layers constituting the unit color sensitive emulsion layer is the most
It is preferable that it exists in the position away from the support body. More
Preferably, in the emulsion layer constituting the light-sensitive material of the present invention.
Therefore, it exists at a position farthest from the support. The content of the first emulsion in the light-sensitive material
(If the first emulsion is added to multiple layers,
(Addition amount) is 0.1 g / m in terms of Ag.²2.0 g / m²
Or less, preferably 0.2 g / m²1.5 or more
g / m²More preferably, it is as follows. Next, it can be used in the light-sensitive material of the present invention.
The second emulsion will be described. In the photosensitive material of the present invention,
Providing a layer containing non-imaged silver halide grains
You can. Non-image-forming silver halide tabular grains are specific
Specifically, the average grain thickness is 0.2 μm or less, and the average silver iodide
The content is preferably 3 mol% or less. The particle thickness is
0.02 μm to 0.2 μm is preferable, 0.05 μm
m or more and 0.15 μm or less are more preferable. Particle size
(Equivalent sphere diameter) is preferably 0.05 μm or more and 2.0 μm or less.
Further, it is more preferably 0.1 μm or more and 1.5 μm or less.
The average silver iodide content of the silver halide grains is
3 mol% or less is preferable, and 2 mol% or less is more preferable.
Preferably, 0 mol% is most preferable. Also contains silver chloride
The rate is preferably 0 mol% or more and 60 mol% or less, and 0 mol%
% To 30 mol% is more preferable. No image formation
Silver halide emulsions are basically not subjected to chemical image processing.
It is preferable to stabilize the dye and silver halide grains.
Therefore, a silver halide adsorbing material may be adsorbed. The layer containing the second emulsion of the present invention is
A layer containing a light first emulsion (milk according to claim 1 of the present invention)
It is not necessary to be adjacent to the agent layer), but it is adjacent
Is preferred and is supported for the emulsion layer according to claim 1 of the present invention.
It is preferable to be arranged close to the body. In non-image forming silver halide emulsion layers
Silver halide grains that do not form an image are expressed in terms of Ag.
Addition) 0.1g / m²2.0 g / m or more²This includes
And preferably 0.2 g / m²1.0 g / m or more²The following is further
preferable. Non-image-forming silver halide tabular grains are disclosed in JP
2000-305228 and JP-A 2000-31
As described in No. 4940
You may set the thickness of a tabular grain so that it may irradiate. concrete
In the present invention, an emulsion layer that does not form an image is adjacent to the indicator side.
A layer containing the first emulsion (emulsion layer according to claim 1)
A flat surface with a thickness that gives strong reflection in the wavelength range to be exposed.
Plate particles may be used. However, the specific wavelength like this
It is not necessary to set the thickness so as to reflect the light. Next, the first emulsion of the present invention described above is preferred.
Method for preparing silver halide grains that can be applied to each other
Will be described in more detail. As the preparation process of the present invention
Is the base part formation step ((a) step), followed by
It consists of an outer shell forming step (step (b)). fundamentally
(A) Only the process may be used, but (a)
(B) It is more preferable to perform a process. (B) Step and
(B1) Dislocation introduction process, (b2) Corner part dislocation limit
The constant introduction process, (b3) the epitaxial bonding process
Yes, either process may be used. First, the base part will be described. Base part
May be 100% of the total silver used for grain formation.
However, it is preferably 50% or more and 95% or less,
More preferably, it is 0% or more and 90% or less. In addition, the base part silver
The average iodine content with respect to the amount is 5 mol% or more.
The following is preferable, but 7 mol% or more and 30 mol% or less are further
preferable. In addition, the base part has a core / shell structure as necessary.
You may take a structure. At this time, the core part of the base part
50% or more and 90% or less of the total silver amount is preferred
The average iodine composition of the core is 5 mol% or more and less than the solid solution limit.
Lower is preferable, and more preferably 7 mol% or more and 30 mol% or less.
Good. On the other hand, the iodine composition of the shell part is 0 mol% or more and 5 mol%.
% Or less is preferable, and 3 mol% or less is more preferable. Next, (a) the process of forming the base part
The process will be described. The formation process of the base part is generally
Well-known process in the field, ie nucleation process
Manufacturing through the process of aging process-growth process
it can. For example, nucleation, ripening, growth, and each process
Is described in detail in Japanese Patent Application Laid-Open No. 2001-92057.
The The protective coating used in the preparation of the emulsion of the present invention.
As the Lloyd, it is advantageous to use the gelatin described above.
However, other hydrophilic colloids can be used.
The For example, gelatin derivatives, gelatin and other polymers
Proteins such as albumin and casein
White matter; hydroxyethyl cellulose, carboxymethyl
Cellulose like cellulose, cellulose sulfates
Sugars such as glucose derivatives, sodium alginate, starch derivatives
Derivatives; polyvinyl alcohol, polyvinyl alcohol
Partial acetal, poly-N-vinylpyrrolidone, polya
Crylic acid, polymethacrylic acid, polyacrylamide, poly
Like Rivinylimidazole, Polyvinylpyrazole
A variety of synthetic hydrophilic polymers such as mono- or copolymers
Quality can be used. The emulsion of the present invention is washed with water for desalting, and fresh.
It is preferable to disperse in a prepared protective colloid.
Gelatin is used as the protective colloid, but zera
Natural polymers and synthetic polymers other than tin are also used.
The The types of gelatin include alkali-treated gelatin,
Oxidation of methionine group in gelatin molecule with hydrogen peroxide
Oxidized gelatin (methionine content 40μmol / g or less)
Lower), amino group-modified gelatin of the present invention (eg, phthalate)
Gelatin, trimellitated gelatin, succinylated gelatin
, Maleated gelatin, esterified gelatin)
It is done. Also, if necessary, JP-A-11-237704
Molecules measured by the paggy method
30% or more of components with a molecular weight of 280,000 or more in the quantity distribution
You may use the lime processing bone gelatin which contains. Also, compare
For example, European Patent No. 758758 and US Patent No. 57
Starch described in No. 33718 may be used. So
In addition, natural polymer is Japanese Patent Publication No.7-111550, Lisa
J Disclosure Vol.176, No.17643 (1978 1
(February) in section IX. Washing temperature depends on purpose
However, it is preferable to select it in the range of 5 ° C to 50 ° C.
Yes. The pH at the time of washing can be selected according to the purpose.
It is preferable to choose. More preferably in the range of 3-8
is there. The pAg at the time of washing can also be selected according to the purpose, but 5-10
It is preferable to choose between. Noodle water as a washing method
Washing method, dialysis method using semipermeable membrane, centrifugal separation method, coagulation sedimentation
Method, ion exchange method, ultrafiltration method
be able to. In the case of coagulation sedimentation, use of sulfate
Method, using organic solvent, using water-soluble polymer
Method, method using gelatin derivatives, etc.
Yes. When forming the particles of the present invention, for example,
Kaihei 5-173268, 5-173269, 5
-173270, 5-173271, 6-20
Polyamides described in Nos. 2258 and 7-175147
Lucylene oxide block copolymer or for example
Polyalkylene described in Japanese Patent No. 3089578
Oxide copolymers may be present. The compound is
It can be any time during particle preparation,
The effect is great when used at an early stage of formation. When preparing the emulsion of the present invention, for example, during grain formation,
During the desalting process, chemical sensitization, there is a metal ion salt before coating.
It is preferable depending on the purpose. Dope particles
In some cases, during particle formation, particle surface modification or chemical sensitization
When used as an agent, added after grain formation and before chemical sensitization
It is preferable to do. When doping the whole particle and the particle
Doping only the core part or the shell part
You can also choose the law. For example, Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b and Bi can be used. These metals are ammo
Nitric acid salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrochloride salt
Or 6-coordination complex salt, 4-coordination complex salt, etc.
Any salt form that can be added can be added. For example,
CdBr₂, CdCl₂, Cd (NO_Three)₂, Pb (N
O_Three)₂, Pb (CH_ThreeCOO)₂, K_Four[Fe (C
N)₆], (NH_Four)_Four[Fe (CN)₆], K₂IrC
l₆, (NH_Four)_ThreeRhCl₆, K_FourRu (CN)₆Gagera
It is. Halo, ako, and shea as ligands for coordination compounds
, Cyanate, thiocyanate, nitrosyl, thioni
You can choose from trosyl, oxo, carbonyl
Yes. These may use only one kind of metal compound,
Two or more kinds may be used in combination. The metal compound is water or methanol, aceto
It is preferable to add it in a suitable organic solvent such as
That's right. Hydrogen halide aqueous solution to stabilize the solution
(Eg HCl, HBr) or halogenated alk
(For example, KCl, NaCl, KBr, NaBr)
The method of adding can be used. Also acid if necessary
・ Alkali may be added. Metal compounds form particles
Even if it is added to the previous reaction vessel, it must be added in the middle of particle formation.
You can also. In addition, water-soluble silver salt (for example, AgNO_Three)is there
Or an aqueous alkali halide solution (for example, NaCl, K
Br, KI) added continuously during silver halide grain formation
It can also be added. Further water-soluble silver salt, halogenated
Prepare a solution independent of the alkali at an appropriate time during particle formation
You may add continuously in a period. Furthermore, various addition methods
It is also preferable to combine them. US Pat. No. 3,772,03
Emulsion tone of chalcogen compound as described in No.1
A method of adding during production may be useful. S, Se, T
In addition to e, cyanate, thiocyanate, selenocyanic acid,
Carbonates, phosphates and acetates may be present. The present invention
Silver halide grains are sulfur sensitized, selenium sensitized, and
Chalcogen sensitization such as Lulu sensitization, gold sensitization, and para
Noble metal sensitization such as palladium sensitization, and low sensitization
At least one step in the production process of silver halide emulsion
Can be applied. Combine two or more sensitization methods
It is preferable. Depending on which process is used for chemical sensitization,
Types of emulsions can be prepared. Inside the particle
A type that embeds the sensitization nucleus, shallow from the particle surface
Type that embeds, or type that creates chemical sensitization nuclei on the surface
There is. The emulsion of the present invention is suitable for the location of chemical sensitization nuclei depending on the purpose.
But generally preferred is near the surface
This is the case when at least one kind of chemical sensitization nucleus is made. Main departure
One chemical sensitization that can be performed clearly and preferably is increased chalcogen.
Sensitization and noble metal sensitization alone or in combination.
(TH James), The Photographic
Process, 4th edition, published by Macmillan, 1977,
(TH James, The Theory of
the Photographic Process,
4th ed, McCillan, 1977) 67-
This can be done using active gelatin as described on page 76.
And research disclosure, 1
Volume 20, April 1974, 12008; Research Day
Closure, 34, June 1975, 1345
2, U.S. Pat. Nos. 2,642,361 and 3,29.
7,446, 3,772,031, 3,8
57,711, 3,901,714, 4,2
66,018, and 3,904,415,
As described in British Patent 1,315,755
PAg 5-10, pH 5-8 and temperature 30-80 ° C
Sulfur, selenium, tellurium, gold, platinum, palladium,
Lithium or a combination of these sensitizers
Can do. In precious metal sensitization, gold, platinum,
Or noble metal salts such as iridium
In particular, gold sensitization, palladium sensitization and the combination of both are preferred.
That's right. In gold sensitization, P.I. Grafkide
by s, Chimie et Physique Pho
tografique (Paul Momtel)
Published, 1987, 5th edition), Research Dis
Closure magazine 307 Volume 307105 etc.
The gold salt that is used can be used. Specifically, chloride
Gold acid, potassium chloroaurate, potassium aurithio
In addition to cyanate, US Pat. No. 2,642,361
No. (gold sulfide, gold selenide, etc.), 3,503,749
No. (thiolate gold with water-soluble group, etc.), 5,04
9,484 (Bis (methylhydantoinato) gold complex
No. 5,049,485 (Mesoionic Thio)
Rate gold complexes such as 1,4,5-trimethyl-1,
2,4-triazolium-3-thiolate gold complex
No. 5,252,455 and 5,391,727
Macrocyclic gold complex, No. 5,620,841,
No. 5,700,631, No. 5,759,760, No.
5,759,761, 5,912,111,
5,912,112, 5,939,245, JP
1-147537, 8-69074, 8-69
075, 9-269554, JP-B 45-292
74, East German Patent DD-264524A, 264
525A, 265474A, 298321A, JP,
2001-75214, 2001-75215,
No. 2001-75216, No. 2001-75217
And gold compounds described in JP-A-2001-75218
Can. The palladium compound is a divalent palladium salt or
Means a tetravalent salt. Preferred palladium compounds are
R₂PdX₆Or R₂PdX_FourIt is represented by Where R is
Represents a hydrogen atom, alkali metal atom or ammonium group
Wow. X represents a halogen atom and represents chlorine, bromine or iodine.
Represents an atom. Specifically, K₂PdCl_Four, (NH_Four)₂
PdCl₆, Na₂PdCl_Four, (NH_Four)₂PdCl_Four, L
i₂PdCl_Four, Na₂PdCl₆Or K₂PdBr_FourPrefer
Good. Gold and palladium compounds are thiocyan
In combination with acid salts or selenocyanates
Yes. In sulfur sensitization, unstable sulfur compounds are added.
Used, P.P. By Grafkides, Chimie et
  Physique Photographic
(Paul Momtel, published in 1987, No. 5
Edition), Research Disclosure Magazine 30
Unstable sulfurization described in Vol. 7, No. 307105, etc.
A compound can be used. Specifically, thiosulfate
(E.g. hypo), thioureas (e.g. diphenylthio)
Aurea, triethylthiourea, N-ethyl-N '-(4
-Methyl-2-thiazolyl) thiourea, dicarboxyme
Til-dimethylthiourea, carboxymethyl-trimethyl
Ruthiourea), thioamides (eg, thioacetamide)
), Rhodanines (eg, diethyl rhodanine, 5
-Benzylidene-N-ethylrhodanine), Phosphi
Sulfides (eg, trimethylphosphine sulfate)
Fido), thiohydantoins, 4-oxo-oxazo
Lysine-2-thiones, disulfides or polysulfurs
Fidos (eg, dimorpholine disulfide, cis
Tin, hexathiocan-thione), mercapto compounds
(Eg cysteine), polythionate, elemental sulfur
Also used are known sulfur compounds such as
Can be. Especially thiosulfates, thioureas, phos
Fin sulfides and rhodanines are preferred. In selenium sensitization, unstable selenium compounds
No. 43-13489, 44-157
48, JP-A-4-25832, and 4-109340.
No., No. 4-271341, No. 5-40324, No. 5
-11385, 6-51415, 6-1752
58, 6-180478, 6-208186
No., No. 6-208184, No. 6-317867, No.
7-92599, 7-98483, 7-140
Use selenium compounds described in No. 579 etc.
You can. Specifically, colloidal metal selenium,
Noureas (eg, N, N-dimethylselenourea, tri
Fluoromethylcarbonyl-trimethylselenourea, a
Cetyl-trimethylselenourea), selenoamides (eg
For example, selenoamide, N, N-diethylphenylseleno
Amide), phosphine selenides (e.g.
Nylphosphine selenide, pentafluorophenyl
Triphenylphosphine selenide), selenophosf
(E.g., tri-p-tolylselenophosphate)
, Tri-n-butylselenophosphate), selenium
No ketones (eg, selenobenzophenone), isose
Lenocyanates, selenocarboxylic acids, selenoeste
(E.g., methoxyphenylselenocarboxy-
2,2-dimethoxycyclohexane ester)
Ruselenides may be used. Furthermore, Japanese Examined Patent Publication No. 46-4553, ibid.
Non-unstable selenium compound described in 52-34492, etc.
Products such as selenious acid and selenocyanic acids (e.g.
Potassium lenocyanate), selenazoles, selenides
Etc. can also be used. In particular, Phosphine Sereni
, Selenoureas, selenoesters and selenocyan
Acids are preferred. In tellurium sensitization, unstable tellurium compounds
JP-A-4-224595, 4-2713
No. 41, No. 4-3333043, No. 5-303157
No. 6-27573, No. 6-175258, No. 6
-180476, 6-208186, 6-20
No. 8184, No. 6-317867, No. 7-14057
Use unstable tellurium compounds described in No. 9 etc.
be able to. Specifically, phosphine tellurides
(For example, butyl-diisopropylphosphine telluride
, Tributylphosphine telluride, tributoxif
Osphintelluride, ethoxydiphenylphosphite
Telluride), diacyl (di) tellurides (eg
(Diphenylcarbamoyl) ditelluride, bis (N-
Phenyl-N-methylcarbamoyl) ditelluride, bis
(N-phenyl-N-methylcarbamoyl) telluride,
Bis (N-phenyl-N-benzylcarbamoyl) tel
Lido, bis (ethoxycarbonyl) telluride), telluro
Ureas (for example, N, N'-dimethylethylenetellurourine)
Elemental, N, N'-diphenylethylenetellurourea) telluro
Amides, telluroesters, and the like may be used. Useful chemical sensitization aids include azaindene,
Chemical sensitization such as azapyridazine and azapyrimidine
To suppress fog and increase sensitivity in the process
Known compounds are used. Examples of chemical sensitization aid modifiers
U.S. Pat. Nos. 2,131,038 and 3,412.
1,914, 3,554,757, JP 58
-126526 and "Photoemulsion Chemistry" by Duffin,
Published by Focal Press (GF Duffin, Pho
tomographic Emulsion Chemis
try, Focal Press, 1966) 138-
Page 143. Gold sensitization used in the present invention
The amount of agent and chalcogen sensitizer used depends on the halogenation used.
Halogenation, depending on silver particles and chemical sensitization conditions
10 per mole of silver ^-8-10^-2Moles, preferably 10^-7
-10^-3It is about a mole. During grain formation of the silver halide emulsion of the present invention,
After grain formation and before or during chemical sensitization
Alternatively, reduction sensitization after chemical sensitization is preferred. here
Reduction sensitization means adding a reduction sensitizer to a silver halide emulsion.
Low pAg atmosphere of pAg1-7 called silver ripening method
A method of growing or aging with care, called high pH aging
Those who grow or mature in a high pH atmosphere of pH 8-11
You can choose any of the laws. Two or more methods
It can also be used together. How to add a reduction sensitizer
This is a preferred method in that the level of original sensitization can be finely adjusted.
is there. Examples of reduction sensitizers include stannous salts,
Ascorbic acid and its derivatives, amines and polya
Mines, hydrazine derivatives, formamidine sulfine
Acids, silane compounds, and borane compounds are known. The present invention
These known reduction sensitizers are selected and used for reduction sensitization.
It is also possible to use two or more compounds in combination.
Yes. Reduction sensitizers include stannous chloride and thiourine dioxide
Elemental, dimethylamine borane, ascorbic acid and its
Derivatives are preferred compounds. The amount of reduction sensitizer added is
Since it depends on the emulsion production conditions, it is necessary to select the addition amount
Is 10 per mole of silver halide.^-7-10^-3Molar range
Is appropriate. The reduction sensitizer is, for example, water or alcohol.
, Glycols, ketones, esters, amides
It is dissolved in an organic solvent such as No. 1 and added during grain growth.
It may be added to the reaction vessel in advance,
A method of adding at an appropriate time is preferable. Also water-soluble silver salt
Or in advance to the water solubility of water-soluble alkali halide
Add a reduction sensitizer and use these aqueous solutions.
Silver halide grains may be precipitated. Also for particle growth
Along with this, the reduction sensitizer solution can be added several times.
It is also a preferable method to add it for a long time. Acid for silver during the production process of the emulsion of the present invention
It is preferable to use an agent. What is an oxidizing agent for silver?
Acts on metallic silver and converts it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very fine silver particles by-produced during chemical sensitization
A compound capable of converting to silver ions is effective. here
The silver ions produced in
It may form a slightly soluble silver salt in water such as silver or silver selenide
It is also possible to form a readily soluble silver salt in water such as silver nitrate.
Yes. The oxidizing agent for silver is organic, even if it is inorganic.
There may be. Examples of inorganic oxidizing agents include ozono
, Hydrogen peroxide and its adducts (eg NaBO₂
・ H₂O₂・ 3H₂O, 2NaCO_Three・ 3H₂O₂, Na_FourP₂
O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ 2H₂O)
Oxalates (eg K₂S₂O₈, K₂C₂O₆, K₂P₂
O₈), Peroxy complex compounds (for example, K₂[Ti (O
₂) C₂O _Four] 3H₂O, 4K₂SO_Four・ Ti (O₂) OH
・ SO_Four・ 2H₂O, Na_Three[VO (O₂) (C₂H_Four)₂]
・ 6H₂O), permanganate (eg KMnO)_Four),
Chromate (eg K₂Cr₂O₇) Like oxygen acid
Salts, halogen elements such as iodine and bromine, perhalogenates
(For example, potassium periodate), high valent metal salts
(Eg, potassium hexacyanoferric acid) and thio
There is a sulfonate. In addition, as an organic oxidizing agent,
quinones such as p-quinone, peracetic acid and perbenzoic acid
Organic peroxides, compounds that release active halogens (eg
For example, N-bromosuccinimide, chloramine T, chloro
Lamin B) is given as an example. Preferred oxidizing agents of the present invention are ozone and peracid.
Hydrogen fluoride and its adducts, halogen elements, thiosulfo
Inorganic oxidizers of phosphates and organic oxidants of quinones.
It is preferable to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver.
This is a new aspect. Apply reduction sensitization after using an oxidizing agent
Method, the reverse method, or both
You can choose from among them. These methods are
Select and use in both particle formation process and chemical sensitization process
it can. The photographic emulsion used in the present invention contains a photosensitive material.
Prevents fogging during the production process, storage, or photo processing
To stop or stabilize photographic performance,
Compounds can be included. Ie thiazole
Such as benzothiazolium salt, nitroimidazole
, Nitrobenzimidazoles, chlorobenzimi
Dazoles, bromobenzimidazoles, mercapto
Thiazoles, mercaptobenzothiazoles, merca
Putobenzimidazoles, mercaptothiadiazoles
, Aminotriazoles, benzotriazoles, di
Trobenzotriazoles, mercaptotetrazoles
(Especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; examples
For example, a thioketo compound such as oxadrine thione;
Zaindenes, such as triazaindenes, tetraa
Zaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes), Pentaazaindene
Known as antifoggants or stabilizers, such as
Many compounds can be added. For example, US patents
3,954,474, 3,982,947,
Use the one described in Japanese Patent Publication No. 52-28660.
You can. One preferred compound is disclosed in JP-A-63-21.
There are compounds described in No. 2932. Antifogging agent
And stabilizers before and during particle formation, after particle formation,
During the washing process, after dispersion with water, before chemical sensitization, during chemical sensitization,
After sensitization, add according to purpose at various times before application
can do. Add to the original fog during emulsion preparation
In addition to preventing and stabilizing,
Control, reduce particle size, reduce particle solubility
Control, chemical sensitization, control dye sequence
It can be used for various purposes. The photographic emulsion used in the present invention has a methine color.
The effect of the present invention is spectral sensitization by elements and others
Is preferable. The dye used is cyani
Dye, merocyanine dye, composite cyanine dye, composite dye
Russianine dye, holopolar cyanine dye, hemicia
Nin dye, styryl dye and hemioxonol dye
Is included. Particularly useful dyes are cyanine dyes, merosi
Dyes belonging to anine dyes and complex merocyanine dyes
It is. These dyes have a basic heterocyclic nucleus as
Any of the nuclei normally used for anine pigments can be applied.
The That is, for example, pyrroline nucleus, oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole
Nucleus, selenazole nucleus, imidazole nucleus, tetrazole
Nucleus, pyridine nucleus; alicyclic hydrocarbon ring fused to these nuclei
Nuclei; and aromatic nuclei fused to these nuclei
Nucleus, for example, indolenine nucleus, benzoindoleni
Nucleus, indole nucleus, benzoxador nucleus, naphtho
Xazole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, benzimidazole nucleus, key
Norin nucleus is applicable. These nuclei are substituted on carbon atoms
It may have a group. Merocyanine dyes or complex
Russianine dyes have nuclei with ketomethylene structure.
For example, pyrazolin-5-one nucleus, thiohydantoy
Nucleus, 2-thiooxazolidine-2,4-dione nucleus,
Azolidine-2,4-dione nucleus, rhodanine nucleus, thiova
It is possible to apply 5-6 membered heterocyclic nucleus of rubituric acid nucleus
Yes. These sensitizing dyes may be used alone.
However, combinations of these may be used, and combinations of sensitizing dyes
Is often used for the purpose of supersensitization. That generation
Examples are U.S. Pat. Nos. 2,688,545 and 2,973.
No. 7,229, No. 3,397,060, No. 3,5
22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No.
3,666,480, 3,672,898,
No. 3,679,428, No. 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
No. 7, British Patent No. 1,344,281, No. 1,50
7,803, Japanese Examined Sho 43-4936, 53-12
No. 375, JP-A 52-110618, 52-10
No. 9925. Along with sensitizing dyes, it
Real dye or visible light that does not have its own spectral sensitization
A substance that does not absorb light and exhibits supersensitization
You may include in an agent. The timing for adding the sensitizing dye to the emulsion is as follows.
Any stage of emulsion preparation known to be useful until
It may be. Most commonly after chemical sensitization is completed
Although it is performed before the cloth, U.S. Pat. No. 3,62
Described in 8,969 and 4,225,666
Spectral sensitization added at the same time as chemical sensitizers
Can be performed simultaneously with chemical sensitization.
Prior to chemical sensitization as described in 928
Completion of precipitation of silver halide grains
Spectral sensitization can be started by adding before. Furthermore
As taught in US Pat. No. 4,225,666
Adding these compounds separately to each other.
Add some of these compounds prior to chemical sensitization,
It can also be added after chemical sensitization.
Including the method disclosed in US Pat. No. 4,183,756.
Any time during the formation of silver halide grains may be used.
The amount added is 4 x 10 per mole of silver halide.^-6~ 8x
10^-3Can be used in moles. Fragmentable electron donating sensitizer
It is also good to use. An electron donating sensitizer is disclosed in U.S. Pat.
5,747,235, 5,747,236,
6,054,260, 5,994,051, European special
No. 788662A1, 893732A1, JP-A-2
000-181001, 2000-180999
No., 2000-181002, 2000-181
No.000, No.2000-221626, No.2000-
No. 221628. Fragmentable
These electron-donating sensitizers can be used anywhere in the photosensitive material manufacturing process.
You can also use it. For example, during grain formation, desalting process,
At the time of academic sensitization and before application. Also, during these processes
It can also be added in several batches. Compounds of the invention
Water soluble solvents such as water, methanol, ethanol
It is also preferable to add it by dissolving in these mixed solvents.
Yes. When dissolving in water, the pH should be higher or lower
For compounds with increased solubility, increase or decrease pH
This may be dissolved and added. Fragmentation
Possible electron donating sensitizers are preferably used in the emulsion layer.
Preferably, it is added to the protective layer and intermediate layer along with the emulsion layer.
Or may be diffused during application. Addition of compounds of the invention
The timing is preferably before or after the sensitizing dye.
1 x 10 per mole of silver halide^-9~ 5x10^-2Mole,
More preferably 1 × 10 ^-8~ 2x10^-3In the proportion of moles
It is contained in the silver halide emulsion layer. Fragmentable power
When using child-sensitizing sensitizers, use preservatives.
And are preferred. Preservative improvers are disclosed in JP-A-11-1193.
64 and JP-A-2001-42466.
It is preferable to use a compound. The silver halide color photographic light-sensitive material of the present invention
2 or more color sensitive layers with different sensitivities on the support
Unit blue-sensitive layer, unit green-sensitive layer, and unit
A silver halide emulsion layer may be used as long as a red sensitive layer is provided.
The number of layers and the order of the non-photosensitive layers satisfy the above requirements.
There are no particular restrictions. A typical example is a sense of unit
The arrangement of the light-sensitive layer is the unit red-sensitive layer, unit from the support side
The green sensitive layer and the unit blue sensitive layer are installed in this order. But eyes
Even if the installation order is reversed, the same color sensitivity
The order of installation is as if different photosensitive layers were encased in the layers.
obtain. Between and above the silver halide photosensitive layer described above.
Provide a non-photosensitive layer such as an intermediate layer for each layer on the upper and lower layers.
Also good. In the intermediate layer, JP-A-61-43748,
59-113438, 59-113440, 6
Described in 1-20037 and 61-20038
Such couplers, DIR compounds may be included,
It may contain a color mixing inhibitor as commonly used. A plurality of halogens constituting each unit photosensitive layer
For silver halide emulsion layers, see German Patent 1,121,470.
Is highly sensitive as described in British Patent No. 923,045
A two-layer structure consisting of an emulsion layer and a low sensitivity emulsion layer is preferably used.
You can. Normally, the photosensitivity decreases gradually toward the support.
It is preferable to arrange so that
A non-photosensitive layer may be provided between the layers. Also,
JP-A-57-112751 and 62-200350
No. 62-206541, 62-206543
Low sensitivity milk on the side away from the support as described in
A high-sensitivity emulsion layer may be installed on the side close to the agent layer and support.
Yes. As a specific example, from the side farthest from the support,
For example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer
(BH) / High-sensitivity green photosensitive layer (GH) / Low-sensitivity green photosensitive layer
Layer (GL) / high sensitivity red light sensitive layer (RH) / low sensitivity red light sensitive
Order of functional layer (RL), or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH. In addition, Shoko 55-
As described in Japanese Patent No. 34932, from the support
Blue photosensitive layer / GH / RH / GL / RL from the farthest side
They can also be arranged in order. JP-A-56-2573
8 and 62-63936.
In addition, the blue-sensitive layer / GL / R from the side farthest from the support
It can also be installed in the order of L / GH / RH. Also described in Japanese Patent Publication No. 49-15495.
As the upper layer, the most sensitive silver halide emulsion
Silver halide emulsions with lower photosensitivity for layers and middle layers
Silver halide milk whose layer and lower layer have lower photosensitivity than the middle layer
The agent layer is arranged, and the photosensitivity is gradually lowered toward the support.
An array composed of three layers with different photosensitivity
The When composed of three layers with different sensitivities
However, it is described in JP-A-59-202464.
In the same color-sensitive layer, from the side away from the support
Arrange in order of medium sensitivity emulsion layer / high sensitivity emulsion layer / low sensitivity emulsion layer
May be. Others, high sensitivity emulsion layer / low sensitivity emulsion layer /
Medium sensitivity emulsion layer or low sensitivity emulsion layer / Medium sensitivity emulsion layer /
They may be arranged in the order of high sensitivity emulsion layers. Also,
Even in the case of four or more layers, the arrangement may be changed as described above. The first emulsion of the present invention comprises any color sensitive layer of milk.
The emulsion layer may be used in the photosensitive layer.
Can be placed anywhere, but blue, green, or red
In the photosensitive layer, the farthest from the support
It is preferable that at least one photosensitive
Placed farthest from the support in the active layer
It only has to be. Furthermore, in all photosensitive emulsion layers
Located farthest from the support
Is preferred. In addition, halogen that does not form an image after exposure processing.
Including an emulsion containing silver halide tabular grains (second emulsion of the present invention)
You may arrange | position the layer which has. This emulsion layer is the
Adjacent to a layer containing one emulsion (emulsion layer according to claim 1)
It does not have to be, but it is better to be adjacent,
The emulsion layer according to claim 1 of the present invention is close to the support.
It is preferable to arrange | position. Specifically, do not image.
2. The emulsion layer according to claim 1, wherein the emulsion layer is adjacent to the indicator side.
Thickness that gives strong reflection in the wavelength range where the emulsion layer is sensitive
You may use the tabular grain with. However, special
The thickness need not be set so as to reflect a constant wavelength. The light-sensitive material according to the present invention includes the above-mentioned various materials.
Other additives, but other than these,
Various additives can be used. These additives are
For more information, Research Disclosure Item
17643 (December 1978), Item 18
716 (November 1979) and Item 30
8119 (December 1989).
The corresponding points are summarized in the table below.     Additive type RD17643 RD18716 RD308119    1 Chemical sensitizer page 23 page 648 right column page 996    2 Sensitivity increasing agent Same as above    3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998, right       Supersensitizer 649, right column on page 649    4 Brightener 24 pages 647 right column 998 right    5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right       And stabilizer    6 Light absorber, pages 25-26, page 649, right column-1003 left-1003 right       Filter dye, page 650, left column       UV absorber    7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right    8 Dye image stabilizer 25 page 1002 right    9 Hardener page 26 page 651 left column 1004 right to 1005 left   10 Binder page 26 Same as above 1003 right to 1004 right   11 Plasticizer, Lubricant 27 pages 650 right column 1006 left to 1006 right   12 Application aid, pages 26-27 Same as above 1005 left-1006 left       Surfactant   13 Static 27 pages Same as above 1006 Right to 1007 Left       Anti-blocking agent   14 Matting agent 1008 left to 1009 left Also, photographic properties with formaldehyde gas
In order to prevent degradation of performance, U.S. Pat. No. 4,411,98
Formua described in No. 7 and No. 4,435,503
A compound that reacts with aldehyde to be immobilized can be used as a photosensitive material.
It is preferable to add. Various color couplers are used in the present invention.
An example of this can be found in the previous research disc.
Roger No. 17643, VII-C to G, and N
o. 307105, described in patents described in VII-CG
Has been. As a yellow coupler, for example,
Allowed 3,933,501, 4,022,620
No. 4,324,024 No. 4,401,75
No. 2, No. 4,248,961, JP-B 58-107
No. 39, British Patent No. 1,425,020, No. 1,4
76,760, US Pat. No. 3,973,968, the same
No. 4,314,023, No. 4,511,649,
Preferred are those described in European Patent No. 249,473A, etc.
That's right. As a magenta coupler, 5-pyrazolone
And pyrazoloazole-based compounds are preferred.
Allowed 4,310,619, 4,351,897
No., European Patent No. 73,636, US Patent No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (1984, 6
Moon), JP-A-60-33552, Research Disc
Roger No. 24230 (June 1984), JP
60-43659, 61-72238, 60-
35730, 55-118034, 60-18
No. 5951, US Pat. No. 4,500,630, No.
No. 4,540,654, No. 4,556,630, country
Particularly preferred are those described in International Publication WO88 / 04795.
That's right. Cyan couplers include phenolic and
Naphthol couplers, US Pat. No. 4,0
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No.
2,369,929, 2,801,171,
Nos. 2,772,162, 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent
121,365A, 249,453A, US
Patents 3,446,622 and 4,333,999
Nos. 4,775,616, 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212, 4,296,
No. 199, JP-A 61-42658, etc.
preferable. Typical of polymerized dye-forming couplers
Examples are U.S. Pat. Nos. 3,451,820 and 4,084.
No. 0, 211, No. 4,367, 282, No. 4, 4
09,320, 4,576,910, British patent
No. 2,102,137, European Patent No. 341,188A
In the issue. Coloring dye has moderate diffusivity
As couplers, U.S. Pat. No. 4,366,237,
British Patent 2,125,570, European Patent 96,5
No. 70, West German Patent (Public) No. 3,234,533
The listed ones are preferred. Color for correcting unwanted absorption of coloring dyes
Coupler is a Research Disclosure No.
No. 17643, VII-G, No. 307105 VII-G
, U.S. Pat. No. 4,163,670, JP-B 57-3
No. 9413, US Pat. No. 4,004,929, No.
No. 4,138,258, British Patent No. 1,146,368
Are preferred. U.S. Pat.
Fluorescence emitted during coupling described in No. 4,181
Couplers that correct unnecessary absorption of coloring dyes with dyes,
The developing agent described in US Pat. No. 4,777,120
A dye precursor group capable of forming a dye in response to a leaving group
It is also preferable to use a coupler having Residues that are photographically useful with coupling
Compounds that release can also be preferably used in the present invention.
The DIR coupler that releases the development inhibitor is the RD1 described above.
7643, VII-F and No. 307105, VII −
Patents described in Section F, Japanese Patent Application Laid-Open No. 57-151944,
57-154234, 60-184248,
63-37346, 63-37350, US Patent
Nos. 4,248,962 and 4,782,012
What has been described is preferred. Nucleating agent or development acceleration in the form of an image during development
As a coupler for releasing the agent, British Patent No. 2,09
7,140, 2,131,188, JP 59
-157638, 59-170840
Is preferred. JP-A-60-107029, the same as above.
60-252340, JP-A-1-44940, 1
-Redox with an oxidized form of the developing agent described in No. -45687
Depending on the reaction, fogging agent, development accelerator, silver halide dissolved
Also preferred are compounds that release agents and the like. In addition, it can be used for the light-sensitive material of the present invention.
Possible compounds include US Pat. No. 4,130,427.
Competitive couplers described in US Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
Multi-equivalent couplers described in No. 618, etc., JP-A-60-18
DI described in No. 5950, JP-A No. 62-24252, etc.
R redox compound release coupler, DIR coupler release
Coupler, DIR coupler release redox compound
Is a DIR redox release redox compound, European Patent No.
173,302A and 313,308A
A coupler that releases a dye that recovers color after release, RD. No. 1
1449, 24241, JP-A-61-2012247
Bleach accelerator releasing couplers described in US Pat.
Patent application title: Ligand-releasing coupler described in Japanese Patent No. 55,477
A leuco dye releasing agent described in JP-A-63-75747
Fluor, described in US Pat. No. 4,774,181
Examples include couplers that release a dye. There are various known couplers used in the present invention.
It can be introduced into the light-sensitive material by the dispersion method. Oil-in-water dispersion
Examples of high boiling solvents used in the process are, for example, U.S. Pat.
No. 2,322,027. Oil-in-water dispersion
High boiling point of 175 ° C or higher at normal pressure
Specific examples of organic solvents include phthalates (for example,
Dibutyl phthalate, dicyclohexyl phthalate
, Di-2-ethylhexyl phthalate, decyl phthalate
And bis (2,4-di-tert-amylphenyl)
Phthalate, bis (2,4-di-tert-amylphe)
Nyl) isophthalate, bis (1,1-diethylpropiyl)
Phthalate); esters of phosphoric acid or phosphonic acid
(Eg triphenyl phosphate, tricresyl
Phosphate, 2-ethylhexyl diphenyl phosphate
, Tricyclohexyl phosphate, tri-2-eth
Tylhexyl phosphate, tridodecyl phosphate
, Tributoxyethyl phosphate, trichloropro
Pyrphosphate, di-2-ethylhexylphenylphosphate
Benzoates); benzoates (eg 2-ethyl)
Ruhexyl benzoate, dodecyl benzoate, 2-
Ethylhexyl-p-hydroxybenzoate);
(E.g., N, N-diethyldodecanamide, N,
N-diethyllaurylamide, N-tetradecylpyrrole
Don); alcohols or phenols (eg
Sostearyl alcohol, 2,4-di-tert-amino
Ruphenol); aliphatic carboxylic acid esters (eg
For example, bis (2-ethylhexyl) sebacate, diocti
Ruazelate, glycerol tributyrate, isostere
Allyl lactate, trioctyl citrate); anili
Derivatives such as N, N-dibutyl-2-butoxy-
5-tert-octylaniline); hydrocarbons (eg
Paraffin, dodecylbenzene, diisopropyl na
Phthalene). Also as an auxiliary solvent
For example, the boiling point is about 30 ° C. or higher, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C or lower can be used.
For example, ethyl acetate, butyl acetate, propio
Ethyl acetate, methyl ethyl ketone, cyclohexanone,
2-Ethoxyethyl acetate, dimethylformamide
Is mentioned. Latex dispersion process steps, effects and implications
Specific examples of immersion latex include, for example, US Pat. No. 4,1.
99,363, West German Patent Application (OLS) No.2,54
Nos. 1,274 and 2,541,230
Has been. In the color light-sensitive material of the present invention, phenethyl is used.
Alcohol, JP-A 63-257747, 62-
Described in No. 272248 and JP-A-1-80941
Of, for example, 1,2-benzisothiazoline-3-
N-butyl-p-hydroxybenzoate, phenol
4-chloro-3,5-dimethylphenol, 2-
Phenoxyethanol, 2- (4-thiazolyl) benzo
Add various preservatives or antifungal agents such as imidazole
It is preferable to add. The present invention is applied to various color light-sensitive materials.
be able to. For example, general or movie colors
Color film for negative film, slide or TV
Transfer film, color paper, color positive film and
And color reversal paper
The The present invention is also particularly preferred for color duplication films.
Can be used. Suitable supports that can be used in the present invention are, for example,
RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column, and
No. 307105, page 879. Main departure
The silver coating amount of the bright photosensitive material is 10.0 g / m²The following is preferred
Preferably, 8.0g / m ²The following is more preferable. The light-sensitive material of the present invention comprises a side having an emulsion layer.
The total dry film thickness of all hydrophilic colloid layers is 28μm or less
Preferably, there is more preferably 23 μm or less, 1
8 μm or less is more preferable, and 16 μm or less is particularly preferable.
Yes. Per emulsion layer containing the first emulsion of the present invention
The dry film thickness is preferably 3.0 μm or less, and 2.5 μm or less.
Further preferred. Dry film thickness is 25 ° C and relative humidity 55
% Is the thickness measured after holding for 2 days or more. Main departure
In a photosensitive material having at least one layer of a bright first emulsion
The water swelling speed is 1/40 (sec^-1)
Better balance of blue, green and red photosensitive layers
And high sensitivity. In the present invention, the upper limit of the water swelling rate
Is not particularly limited as long as the effect of the present invention is exhibited,
/ 20 (sec^-1The following are preferred. In the present invention, “water swelling speed T” means halo.
Immerse the silver halide photographic material in distilled water at 20 ° C for 5 minutes.
The swelling rate at the time (hereinafter defined as “water swelling rate”) is 1.
It is defined as the reciprocal of the time (seconds) to reach 25%. Main departure
In light, the water swelling rate is preferably 1/45 or more.
/ 40 or more is more preferable. What is “water swelling rate”?
/ D) × 100 [%]. ΔD is due to the above water swelling.
D is the dry film thickness.
The film swelling film thickness is determined according to a method known in the art.
For example, A. Green (A. Gr
een) et al.
And engineering (Photogr. Sci. E
ng. ), Vol. 19, No. 2, pages 124-129
Measured by using a spherometer (swelling meter)
it can. The water swelling rate is determined by gelatin as a binder.
Add a hardener to the skin, or
It can be adjusted by changing. Hardener is
Inorganic or organic gelatin hardeners alone or in combination
And add as appropriate to each layer of the multilayer coated photosensitive material.
Thus, the swelling speed can be controlled. like that
Hardeners are those described above and Kenneth Mason Public
ations, Ltd., Dudley Annex, 12 North Street, Emswo
September 1996 by rth, Hampshire P010 7DQ, ENGLAND
Research Disclosure published in (ResearchDis
closure) No. 38957, pages 599-600
The In the present invention, vinyl is preferable as a hardener.
It is a sulfonyl compound. Such compounds can have multiple
It is characterized by containing a nylsulfonyl group. Jibi
In nylsulfone, there are two single sulfonyl groups
Bonded to vinyl base. Multiple vinylsulfonyl esters
Alkyl groups such as vinylsulfonylmethyl, vinylsulfur
Honylethyl, vinylsulfonylpropyl or vinyl
Ether, amine, dia mediated by sulfonylbutyl group
They are linked through a min or hydrocarbon bond. Screw
(Vinylsulfonyl) ether, for example bis (vinyls)
Sulfonylmethyl) ether and bis (vinylsulfone)
Ruethyl) ether, N, N-methylene-bis ((β-vinyl
Sulfonyl) propionamide) is particularly preferred. Typical
Vinylsulfonyl hardeners and their synthesis and use
Procedure for use is US Patent 3,490,911, US Patent
No. 3,539,644, disclosed in U.S. Pat.No. 3,642,486
Has been. Other methods of controlling the water swelling rate of the photosensitive layer
Add a hydrophilic polymer to increase its swelling rate,
Or a polymer hardener, or a hardener-reactive polymer,
Or modified gelatin, such as amine-modified gelatin
It is also possible to control by inserting. Sense of the present invention
The water swelling ratio of the side having the emulsion layer of the optical material is 20% or more and 30
0% or less is preferable, 50% or more and 200% or less is further
preferable. The light-sensitive material of the present invention comprises a side having an emulsion layer.
On the opposite side to the support, the total dry film thickness is 2 μm-2
A 0 μm hydrophilic colloid layer (referred to as a back layer) is provided.
It is preferable. In this back layer, for example, the above-mentioned light
Absorber, filter dye, UV absorber, antistatic
Stopper, hardener, binder, plasticizer, lubricant, coating aid
It is preferable to contain an agent and a surfactant. This bag
The water swelling rate of the ink layer is preferably 50 to 250%. The color photographic light-sensitive material according to the present invention is
RD. No. 17643, pp. 28-29, ibid.
No. 18716, page 651, left column to right column; 30
7105, pages 880-881 in the usual way
Therefore, it can be developed. Of the light-sensitive material of the present invention
The color developer used for the development processing is preferably aromatic first
Alkaline water solution based on secondary amine color developing agent
It is a liquid. As this color developing agent, aminophenol
P-phenylenediamine-based compounds are also useful.
A compound is preferably used.
Til-4-amino-N, N-diethylaniline, 3-methyl
Tyl-4-amino-N-ethyl-N-β-hydroxye
Tyraniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-me
Tyl-4-amino-N-ethyl-β-methoxyethyla
Nilin and their sulfate, hydrochloride or p-tolu
Examples thereof include enesulfonates. Among these, special
3-methyl-4-amino-N-ethyl-N-β-hy
Droxyethylaniline sulfate is preferred. these
Two or more compounds can be used in combination according to the purpose. The color developer is, for example, an alkali metal charcoal.
PH buffering agents such as acid salts, borates or phosphates,
Chloride salt, bromide salt, iodide salt, benzimidazole
Benzothiazoles or mercapto compounds
Such development inhibitors or antifogging agents are generally included.
is there. If necessary, hydroxylamine, diethyl
Hydroxylamine, sulfite, N, N-biscarbo
Hydrazines such as xylmethylhydrazine, phenyl
Micarbazides, triethanolamine, catechols
Various preservatives such as sulfonic acids; ethylene glycol, di
Organic solvents such as ethylene glycol; benzyl alcohol
, Polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines; dye-forming couplers, competition
Couplers such as 1-phenyl-3-pyrazolidone
Auxiliary developing agent; Viscosifier; Aminopolycarboxylic acid, amino
Nopolyphosphonic acid, alkylphosphonic acid, phosphonocar
Use various chelating agents as represented by boric acid
Can do. Examples of chelating agents include ethylene dia
Mine tetraacetic acid, nitrile triacetic acid, diethylenetriamine five
Acetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl
Louisinodiacetic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, nitrilo-N, N, N-trimethylene
Sphonic acid, ethylenediamine-N, N, N, N-tetra
Methylenephosphonic acid, ethylenediamine-di (o-hydride)
Roxyphenylacetic acid) and their salts are typical examples.
I can make it. In addition, when carrying out inversion processing, normally black
Color development is performed after white development. In this black and white developer
For example, dihydroxybens such as hydroquinone
Zens such as 1-phenyl-3-pyrazolidone
Such as 3-pyrazolidones or, for example, N-methyl-
Publicity of aminophenols such as p-aminophenol
Use known black and white developing agents alone or in combination
be able to. P of these color developers and black-and-white developers
H is generally 9-12. Also this
The replenishment amount of these developers is the color photographic material to be processed.
However, generally 3 liters per square meter of photosensitive material
Torr (hereinafter, liter is also referred to as “L”)
Yes, keep the bromide ion concentration in the replenisher low.
And 500 milliliters (hereinafter referred to as milliliters)
Also expressed as “mL”. ) You can also: Supplement
When reducing the amount of charge, the contact area of the treatment liquid with air should be
Prevents liquid evaporation and air oxidation by reducing the size.
It is preferable. Contact area between photographic processing solution and air in processing tank
Can be expressed by the aperture ratio defined below. Immediately
The Opening ratio = [contact area between treatment liquid and air (cm²)] ÷ [Process
Capacity of scientific liquid (cm^Three]] The opening ratio is preferably 0.1 or less, more
Preferably it is 0.001-0.05. Open like this
As a method of reducing the percentage, the photographic processing liquid level of the processing tank
In addition to providing a shield such as a floating lid
Using the movable lid described in JP-A-1-82033
The method described in Japanese Patent Application Laid-Open No. 63-2106050
Can be mentioned. Reduces aperture ratio
If only the color development and black-and-white development processes
And subsequent processes such as bleaching, bleach-fixing, fixing, water
It is preferable to apply in all steps of washing and stabilization.
Yes. Means to suppress accumulation of bromide ions in the developer
The amount of replenishment can also be reduced by using. The color development processing time is usually between 2 and 5 minutes.
Set at high temperature, high pH, and high color developing agent
By using it for concentration, the processing time is further shortened.
You can also The photographic emulsion layer after color development is usually bleached.
Is done. The bleaching process may be performed simultaneously with the fixing process.
(Bleaching and fixing) may be performed individually. Further processing
Bleaching and fixing after bleaching to speed up the process
A processing method may be used. In addition, two continuous bleach-fixing baths
Processing before the bleach-fixing process.
Or bleaching after the bleach-fixing process.
Can be implemented at any time. Examples of bleaching agents include iron (II
Compounds of polyvalent metals such as I), peracids (especially
Is suitable for movie color negative film), quinone
Nitro compounds are used. As representative bleach
Is an organic complex salt of iron (III), such as ethylenediamine
Acetic acid, diethylenetriaminepentaacetic acid, cyclohexanedi
Amine tetraacetic acid, methyliminodiacetic acid, 1,3-diamino
Of propanetetraacetic acid, glycol ether diamine tetraacetic acid
Complex salts with aminopolycarboxylic acids such as
Use complex salts with citric acid, tartaric acid, malic acid
Can do. Of these, iron ethylenediaminetetraacetate
(III) Complex salts and iron 1,3-diaminopropanetetraacetate
(III) Aminopolycarboxylic acid irons including complex salts (II
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution.
Yes. In addition, iron (III) complex salts of aminopolycarboxylates
Especially useful in white liquor and bleach-fix solution
The Using these iron (III) complex salts of aminopolycarboxylic acids
The pH of the bleaching solution or bleach-fixing solution is usually from 4.0 to 8.
Can be processed at a lower pH for faster processing.
You can also. For bleaching solutions, bleach-fixing solutions and their pre-baths
If necessary, a bleaching accelerator can be used.
Specific examples of useful bleach accelerators are described in the following specification:
For example: US Pat. No. 3,893,858, West Germany
Patent Nos. 1,290,812 and 2,059,988
, JP-A-53-32736, 53-57831
No., 53-37418, 53-72623,
53-95630, 53-95311, 53-
104232, 53-124424, 53-1.
41623, 53-18426, Research D
Closure No. No. 17129 (July 1978)
Having a mercapto group or disulfide group as described in
Compound: thiazolid described in JP-A No. 51-140129
Derivatives: Japanese Examined Patent Publication No. 45-8506, Japanese Unexamined Patent Publication No. 52-20
No. 832, No. 53-32735, US Pat. No. 3,70
A thiourea derivative described in US Pat. No. 6,561, West German Patent 1,
127,715, described in JP-A-58-16235
Iodide salt; West German Patent No. 966,410, No. 2,74
Polyoxyethylene compounds described in No. 8,430;
A polyamine compound described in JP-A-45-8836;
Other JP-A-49-40943, 49-59644,
53-94927, 54-35727, 55
-26506 and 58-163940
Bromide ions can be used. Among them, mercap
A compound having a thio group or a disulfide group has an accelerating effect
Preferred from a large standpoint, especially US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP 53
The compound described in -95630 is preferable. In addition, the United States
The compounds described in Japanese Patent No. 4,552,884 are also preferred.
Yes. These bleach accelerators may be added to the light-sensitive material. Shoot
When bleach-fixing color light-sensitive materials for shadows, these
Bleach accelerators are particularly effective. In the bleaching solution and bleach-fixing solution, in addition to the above compounds
To contain organic acid for the purpose of preventing bleach stain
It is preferable. Particularly preferred organic acids are acid dissociation constants.
A compound having (pKa) of 2 to 5, specifically,
For example, acetic acid, propionic acid, hydroxyacetic acid
Can do. As a fixing agent used in fixing solutions and bleach-fixing solutions
For example, thiosulfate, thiocyanate, thioether
Tellurium compounds, thioureas, and large amounts of iodide salts
You can. Of these, the use of thiosulfate is common.
In particular, ammonium thiosulfate is most widely used.
The Also, thiosulfate and, for example, thiocyanate, thiocyanate
A combined use of an ethereal compound and thiourea is also preferred. Fixing
As preservatives for liquids and bleach-fixing solutions, sulfites and bisulfites
Salt, carbonyl bisulfite adduct or European Patent No. 29
The sulfinic acid compounds described in 4,769A are preferred.
Yes. In addition, fixing solutions and bleach-fixing solutions have the purpose of stabilizing the solutions.
Of various aminopolycarboxylic acids and organic phosphonic acids
Addition is preferred. In the present invention, the fixing solution or bleaching constant
The landing liquid has a pKa of 6.0 to 9.0 for pH adjustment.
Compounds, preferably imidazole, 1-methylimidazo
, 1-ethylimidazole, 2-methylimidazole
0.1-10 mol / L of imidazole such as
It is preferable. The total time of the desilvering process is the result of desilvering failure.
It is preferable that the length is as short as possible. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Also processing temperature
Is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferred temperature range, the desilvering rate is improved and
Stain generation after treatment is effectively prevented. During the desilvering process
Therefore, it is preferable that the stirring is strengthened as much as possible.
Yes. As a concrete method for strengthening stirring, JP-A-62-1
A jet of processing solution on the emulsion surface of the photosensitive material described in No. 83460
And the method of making them collide with each other, as disclosed in JP-A-62-183461.
The method of raising the stirring effect using a rolling means is mentioned. Further
The wiper blade provided in the liquid and the emulsion surface.
Move the photosensitive material while touching it to make the emulsion surface turbulent
To improve the stirring effect and processing
A method of increasing the circulation flow rate of the entire liquid can be mentioned. this
Such a stirring improving means is used for bleaching solution, bleach-fixing solution, fixing solution.
In either case, it is effective. Stirring is improved in the emulsion film.
Accelerate the supply of bleaching agent and fixing agent to the
It is thought to increase the silver speed. Also, the stirring direction
The above measures are more effective when a bleach accelerator is used,
The acceleration effect is remarkably increased or fixed by a bleach accelerator.
The inhibitory action can be eliminated. Automatic used for developing the light-sensitive material of the present invention
Developing machines are disclosed in JP-A-60-191257 and 60-19.
Photosensitive materials described in Nos. 1258 and 60-191259
It is preferable to have a conveying means. The above-mentioned JP-A-6
Such a carrier as described in 0-191257
The stage significantly reduces the amount of processing solution brought from the pre-bath to the post-bath.
Therefore, the effect of preventing the performance deterioration of the processing liquid is high. like this
The main effects are shortening of processing time and replenishment of processing solution in each process.
This is particularly effective for reducing the amount. The silver halide color photographic light-sensitive material of the present invention
After desilvering, it is recommended to go through water washing and / or stabilization process.
It is common. The amount of water washed in the washing process is a characteristic of the photosensitive material.
(For example, depending on the material used such as coupler), application,
Furthermore, for example, the washing water temperature, the number of washing tanks (number of stages),
Depending on replenishment methods such as counterflow and forward flow, and other various conditions
Can be set widely. Of these, the multistage countercurrent method
The relationship between the number of washing tanks and the amount of water is Journal of
  the Society of Motion Pi
cute and Television Engi
neers vol. 64, p. 248-253 (1955
In May). According to the multi-stage countercurrent system described in the above document,
Although the amount of washing water can be greatly reduced, the water in the tank
Increased residence time causes bacteria to propagate and
There arises a problem that the play material adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, such a problem.
As a solution to the problem, described in JP-A-62-288838
Reduces calcium and magnesium ions
The method can be used very effectively. In addition,
For example, isothiazolonation described in No. 57-8542
Compounds, siabendazoles, chlorinated isocyanuric acid
Chlorine disinfectants such as sodium, etc.
Horiguchi Hiroshi, “Anti-bacterial and antifungal agents, like Nzotriazole
Science (1986) Sankyo Publishing, Hygienic Technology Society
Sterilization, sterilization and fouling technology "(1982) Japan Industrial Technology Association, Japan
This edition of the Society for Antibacterial and Antifungal Studies, “Encyclopedia of Antibacterial and Antifungal Agents” (1986)
The described fungicides can also be used. P of washing water in the processing of the light-sensitive material of the present invention
H is 4-9, preferably 5-8. Washing water temperature and
Depending on the characteristics and application of the photosensitive material,
Generally, it can be set, but in general, it is 20 seconds to 1 at 15 to 45 ° C.
0 minutes, preferably 25-40 ° C for 30 seconds to 5 minutes
Selected. Further, the light-sensitive material of the present invention can be used in place of the above water washing.
Alternatively, it can be treated directly with a stabilizing solution. this
In such stabilization treatment, JP-A-57-8543
No. 58-14834, 60-220345
All known methods described can be used. Further, following the water washing treatment, further stabilization
Sometimes it is processed. An example of this is color photography for photography.
Dye stabilizers and surface activity used as the final bath of materials
Mention may be made of a stabilizing bath containing a sexing agent. Dye stability
Examples of the agent include formalin and glutaraldehyde.
Aldehydes, N-methylol compounds, hex
Samethylenetetramine or aldehyde sulfite addition
You can list things. In this stable bath,
Toning agents and fungicides can be added. Washing with water and / or
The overflow liquid that accompanies the replenishment of the stabilizer is the desilvering process
It can be reused in other processes. For example
In processing using an automatic processor, each of the above processing solutions is steamed.
When concentrating with water, correct the concentration by adding water.
It is preferable. The silver halide color photographic light-sensitive material of the present invention
In order to simplify and speed up processing,
It may be built in. To incorporate, color developing agent
It is preferable to use various precursors. For example, rice
Indoaniline system described in Japanese Patent No. 3,342,597
Compound, for example, 3,342,599, Research
・ Disclosure No. 14,850 and No.
No. 15,159, Schiff base type compounds, 1
Aldol compounds described in US Pat. No. 3,924, US Pat.
719,492, a metal salt complex described in JP-A-53-1
Examples include urethane compounds described in No. 35628
it can. The silver halide color light-sensitive material of the present invention is
If necessary, various types of 1-
Phenyl-3-pyrazolidones may be incorporated. Typical
Examples of such compounds are disclosed in, for example, JP-A-56-64339.
57-144547 and 58-115438
It is described in. The various processing liquids in the present invention are 10
Used at -50 ° C. Usually 33 ° C-38 ° C
The temperature of the standard is standard, but the temperature can be increased to accelerate the process.
Reduce processing time or conversely lower temperature to improve image quality
And the stability of the treatment liquid can be improved. The silver halide light-sensitive material of the present invention is
U.S. Pat. No. 4,500,626, JP-A-60-133
449, 59-218443, 61-2380
56, European Patent No. 210,660A2, etc.
The present invention can also be applied to photothermographic materials. In addition, the present invention
The silver halide color photographic light-sensitive material of JP-B-2-32
615, No. 3-39784, etc.
More when applied to a lens-equipped film unit.
It is easy to produce effects and is effective. [0098] EXAMPLES The present invention will be specifically described below with reference to examples.
Light up. However, the present invention is limited to these examples.
It is not a thing. Example 1 (Seed emulsion) described in Example 1 of JP-A-11-174606
In emulsion 1C, AgI fine particles during the growth process
Is added to the total amount of silver in the grains after the growth process.
Halogenation by adjusting the silver halide content to 10 mol%
Silver tabular grains were prepared. After washing with water, add gelatin and p
H, 5.7, pAg, 8.8, silver conversion per kg of emulsion
Adjusted to a total mass of 131.8 g and a gelatin mass of 64.1 g
A seed emulsion was obtained. In the resulting emulsion, the silver iodide content
10 mol%, sphere equivalent diameter 0.7μm, aspect ratio 28 grains
The child accounted for 97% of the total projected area. (Em-A1) Trimeritization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 mL of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Corporation product, L7602) 0.3g
Added. H₂SO_FourTo adjust the pH to 5.5
After, AgNO_Three67.6 mL of an aqueous solution containing 7.0 g and K
Double mixed aqueous solution of KBr and KI containing 10 mol% I
The final flow rate is 5.1 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 6 minutes. At this time, silver potential
Was kept at +0 mV to a saturated calomel electrode. Benze
Sodium thiosulfonate 2mg and thiourea dioxide 2
After adding mg, AgNO_ThreeAqueous solution 7 containing 170 g
Mixed aqueous solution of KBr and KI containing 62 mL and 10% KI
The final flow rate is 3.7 times the initial flow rate by the double jet method.
The flow rate was accelerated so as to be added over 120 minutes.
At this time, the silver potential is +10 mV to the saturated calomel electrode.
Kept. AgNO_Three75 mL of aqueous solution containing 23.4 g
And KBr aqueous solution for 11 minutes by double jet method
Added. At this time, the silver potential is + to the saturated calomel electrode.
It was kept at 10 mV. Increase the temperature to 82 ° C and add KBr
After adjusting the silver potential to −80 mV, 0.037 μm grains
A child-size AgI fine grain emulsion was converted into 2.18 in terms of KI mass.
g was added. Immediately after the addition, AgNO_Three23.4
Add 100.2 mL of aqueous solution containing g over 10 minutes
It was. The silver potential is -80 with aqueous KBr solution for the first 5 minutes of addition.
It was kept at mV. After washing with water, add gelatin and
The pH was adjusted to 5.8 and pAg 8.7. Compound 1 and
After adding 2, the temperature was raised to 60 ° C. Sensitizing dye 1 and
After adding 2, potassium thiocyanate, chloroauric acid,
Sodium thiosulfate, N, N-dimethylselenourea
Added and optimally chemically sensitized. Compound 3 at the end of chemical sensitization
And Compound 4 was added. Here, optimal chemical sensitization
Means that sensitizing dyes and each compound are
10 per le^-1To 10^-8Select from a range of molar additions
Means that. [0100] [Chemical 1] [0101] [Chemical 2] [0102] [Chemical 3] [0103] [Formula 4] [0104] [Chemical formula 5] [0105] [Chemical 6] (Em-A2) Trimeritization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 mL of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Corporation product, L7602) 0.3g
Added. H₂SO_FourTo adjust the pH to 5.5
After, AgNO_Three67.6 mL of an aqueous solution containing 7.0 g and K
Double mixed aqueous solution of KBr and KI containing 10 mol% I
The final flow rate is 5.1 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 6 minutes. At this time, silver potential
Was kept at +0 mV to a saturated calomel electrode. Benze
Sodium thiosulfonate 2mg and thiourea dioxide 2
After adding mg, AgNO_ThreeAqueous solution 7 containing 170 g
Final flow rate of 62 mL and KBr aqueous solution by double jet method
The flow rate is increased to 120 times the initial flow rate to 120 times.
Added over a minute. At this time, 0.037 μm at the same time
A grain-size AgI fine grain emulsion having a silver iodide content of 10
At the same time, the flow rate is accelerated so as to be mol% and silver is added.
The potential was kept at -30 mV with respect to the saturated calomel electrode.
AgNO_Three75 mL of aqueous solution containing 23.4 g and KBr water
The solution was added over 11 minutes by the double jet method. This
The silver potential is +10 mV to the saturated calomel electrode
Kept. Increase the temperature to 82 ° C and add KBr to reduce the silver potential.
After adjusting to 80 mV, a particle size of 0.037 μm
Add 2.28 g of AgI fine grain emulsion in terms of KI mass
It was. Immediately after the addition, AgNO_ThreeContains 23.4g
100.2 mL of aqueous solution was added over 10 minutes. Addition
For the first 5 minutes, keep the silver potential at -80 mV with aqueous KBr solution.
It was. After washing with water, gelatin was added and pH 5.
8, adjusted to pAg 8.7. After that, the same as Em-A1
Like, chemical sensitization. (Em-A3) Trimeritization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 mL of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Corporation product, L7602) 0.3g
Added. H₂SO_FourTo adjust the pH to 5.5
After, AgNO_Three67.6 mL of an aqueous solution containing 7.0 g and K
Double mixed aqueous solution of KBr and KI containing 10 mol% I
The final flow rate is 5.1 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 6 minutes. At this time, silver potential
Was kept at +0 mV to a saturated calomel electrode. Benze
Sodium thiosulfonate 2mg and thiourea dioxide 2
After adding mg, A was added to the stirring device installed outside the reaction vessel.
gNO_Three, 170g aqueous solution, 762mL and KBr
107.1 g, KI 16.6 g and molecular weight 20000
762 mL of an aqueous solution containing 76.2 g of gelatin
AgBrI fine particles with a silver iodide content of 10 mol%
While preparing emulsion (average size: 0.015 μm)
Add this AgBrI emulsion to the reaction vessel over 120 minutes
did. At this time, the silver potential is −3 with respect to the saturated calomel electrode.
It was kept at 0 mV. AgNO_ThreeAqueous solution 7 containing 23.4 g
5mL and KBr aqueous solution in 11 minutes by double jet method
Added over. At this time, the silver potential is applied to the saturated calomel electrode.
And kept at +10 mV. Raise the temperature to 82 ° C and add KBr.
To adjust the silver potential to −80 mV, and then 0.037 μm.
mI grain size AgI fine grain emulsion in terms of KI mass
2.28 g was added. Immediately after the addition, AgNO_Three
100.2 mL of an aqueous solution containing 23.4 g was passed over 10 minutes
Added. Silver potential with KBr aqueous solution for the first 5 minutes of addition
Was kept at -80 mV. After washing with water, add gelatin
The pH was adjusted to 5.8 and pAg 8.7 at 40 ° C. That
Thereafter, chemical sensitization was performed in the same manner as Em-A1. (Em-A4) Trimeritization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 mL of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Corporation product, L7602) 0.3g
Added. H₂SO_FourTo adjust the pH to 5.5
After, AgNO_Three67.6 mL of an aqueous solution containing 7.0 g and K
Double mixed aqueous solution of KBr and KI containing 10 mol% I
The final flow rate is 5.1 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 6 minutes. At this time, silver potential
Was kept at +0 mV to a saturated calomel electrode. Benze
Sodium thiosulfonate 2mg and thiourea dioxide 2
After adding mg, A was added to the stirring device installed outside the reaction vessel.
gNO_Three, 170g aqueous solution, 762mL and KBr
107.1 g, KI 16.6 g and molecular weight 20000
762 mL of an aqueous solution containing 76.2 g of gelatin
AgBrI fine particles with a silver iodide content of 10 mol%
While preparing emulsion (average size: 0.015 μm)
Add this AgBrI emulsion to the reaction vessel over 120 minutes
did. At this time, the silver potential is −3 with respect to the saturated calomel electrode.
It was kept at 0 mV. AgNO_ThreeAqueous solution 7 containing 23.4 g
5mL and KBr aqueous solution in 11 minutes by double jet method
Added over. At this time, the silver potential is applied to the saturated calomel electrode.
And kept at +10 mV. Reduce the temperature to 40 ° C and add KBr.
After adjusting the silver potential to -40 mV, p-yodoa
Cetamidobenzenesulfonate (monohydric)
After adding an aqueous solution containing 14.5 g of
Add 57cc of sodium sulfite aqueous solution for 1 minute
And generate iodide ions while controlling the pH to 9.0.
After 2 minutes, heat up to 55 ° C over 15 minutes and then p
Returned H to 5.5. Then AgNO_Three23.4g
An aqueous solution containing 100.2 mL was added over 16 minutes.
During the addition, the silver potential was kept at -50 mV with an aqueous KBr solution.
After washing with water, gelatin was added and the pH was 5.8 at 40 ° C., p.
It adjusted to Ag8.7. After that, the same as Em-A1
I was sensitized. (Em-A5) An emulsion was prepared in the same manner as Em-A4.
Prepared. After adding compounds 1 and 2, the temperature was raised to 60 ° C.
Warm up. After addition of sensitizing dyes 1 and 2, thiocyan
Potassium acetate, bis (1,4,5-trimethyl-1,
2,4-triazolium-3-thiolate gold) (I)
Trifluoroborate, carboxymethyltrimethylthio
Optimum addition of ourea and N, N-dimethylselenourea
Chemical sensitization. Compound 3 and compound at the end of chemical sensitization
4 was added. Here, optimal chemical sensitization means sensitization
10 dyes per mole of silver halide
^-1To 10^-8Means selected from the range of molar addition amount
To do. (Em-A6) The emulsion was prepared in the same manner as Em-A4.
Prepared. After adding compounds 1 and 2, the temperature was raised to 60 ° C.
Warm up. After addition of sensitizing dyes 1 and 2, thiocyan
Potassium acetate, bis (1,4,5-trimethyl-1,
2,4-triazolium-3-thiolate gold) (I)
Trifluoroborate, carboxymethyltrimethylthio
Optimum addition of ourea and N, N-dimethylselenourea
Chemical sensitization. 1 × 10 for compound 5 during chemical sensitization^-Fourmol /
molAg was added. Compound 3 and compound at the end of chemical sensitization
Product 4 was added. Here, optimal chemical sensitization means
1 dye per mole of silver halide
0^-1To 10^-8It means that it was selected from the range of molar addition amount.
Taste. [0111] [Chemical 7] (Em-A7) Trimeritization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 mL of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Corporation product, L7602) 0.3g
Added. H₂SO_FourTo adjust the pH to 5.5
After, AgNO_Three67.6 mL of an aqueous solution containing 7.0 g and K
Double mixed aqueous solution of KBr and KI containing 10 mol% I
The final flow rate is 5.1 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 6 minutes. At this time, silver potential
Was kept at +0 mV to a saturated calomel electrode. Benze
Sodium thiosulfonate 2mg and thiourea dioxide 2
After adding mg, A was added to the stirring device installed outside the reaction vessel.
gNO_Three, 170g aqueous solution, 762mL and KBr
107.1 g, KI 16.6 g and molecular weight 20000
762 mL of an aqueous solution containing 76.2 g of gelatin
AgBrI fine particles with a silver iodide content of 10 mol%
While preparing emulsion (average size: 0.015 μm)
Add this AgBrI emulsion to the reaction vessel over 120 minutes
did. At this time, the silver potential is −3 with respect to the saturated calomel electrode.
It was kept at 0 mV. AgNO_ThreeAqueous solution 1 containing 58.5 g
Mixed water of KBr and KI containing 31 mL and 10 mol% KI
The solution was added over 30 minutes by the double jet method. This
The first 20 minutes of the silver potential relative to the saturated calomel electrode
Keep it at +20 mV for the rest and 120 mV for the remaining 10 minutes
It was. After cooling to 50 ° C., 55 mL of 0.3% KI aqueous solution
Was added over 10 minutes. Immediately thereafter, AgNO
_Three18.8 mL of an aqueous solution containing 8.4 g and 1.4 of NaCl
20 g of an aqueous solution containing 4 g and KBr 2.35 g and AgI
A solution containing 0.005 mol of fine particles was added simultaneously.
At this time, AgNO to be added_Three8.0 for 1 mol
× 10^-Fourmol K_Four[RuCN₆] Was present. That
Later, a sensitizing dye was added (for epitaxial stabilization).
() After washing with water, add gelatin and pH at 40 ° C.
5.8, adjusted to pAg 8.7. Then Em-A6
As well as chemical sensitization. (Em-B) Low molecular weight gelatin 0.96
19.2 mL of an aqueous solution containing g and KBr, 0.9 g
The mixture was kept at ℃ and stirred vigorously. AgNO_Three, 1.49g
An aqueous solution containing 37.5 mL of an aqueous solution containing 1.5 g of KBr
Add 37.5mL over 30 seconds by double jet method
did. After adding 1.2 g of KBr, the temperature was raised to 75 ° C.
Aged. After sufficient aging, the amino group is trimellitic acid
Trimellitized with a molecular weight of 100,000
30 g of latin was added and the pH was adjusted to 7. Dioxide
6 mg of thiourea was added. AgNO_Three29g included
116mL of aqueous solution and aqueous KBr solution by double jet method
Accelerate the flow rate so that the final flow rate is 3 times the initial flow rate.
Added. At this time, the silver potential is −
It was kept at 20 mV. AgNO_Three, Water containing 110.2g
Double jet method with 440.6 mL of solution and aqueous KBr solution
The flow rate is accelerated so that the final flow rate is 5.1 times the initial flow rate.
And added over 30 minutes. At this time, the adjustment of Em-A1
The AgI fine grain emulsion used in the production had a silver iodide content of 1
Add flow rate accelerated to 5.8 mol% at the same time
In addition, the silver potential is kept at 0 mV with respect to the saturated calomel electrode.
It was. AgNO_Three, 26.5 g of aqueous solution 96.5m
Add L and KBr aqueous solution for 3 minutes by double jet method
Added. At this time, the silver potential was kept at 0 mV. Ethylthio
After adding 26 mg of sodium sulfonate, 55 ° C
The silver potential is reduced to -90 mV by adding an aqueous KBr solution.
It was adjusted. The above-mentioned AgI fine grain emulsion is converted into KI mass.
8.5 g was added. Immediately after the addition, AgNO_Three, 5
228 mL of an aqueous solution containing 7 g was added over 5 minutes.
At this time, the potential at the end of the addition becomes +20 mV.
It adjusted with Br aqueous solution. Washed with water in the same way as Em-A1
And chemical sensitization. (Em-C) 35 μmol of meg / g
Thionine-containing phthalation rate of 100,000 and a molecular weight of 9
7% phthalated gelatin 1.02g, KBr 0.97g
Keep 1192 mL of aqueous solution containing 35 ° C and stir vigorously
did. AgNO_ThreeSolution containing 4.47 g, 42 mL
And an aqueous solution containing 3.16 g of KBr, 42 mL
It was added over 9 seconds by the jet method. Add 2.6g of KBr
After the addition, the temperature was raised to 66 ° C. and fully aged. Matured
Later, the molecular weight 100,000 used in the preparation of Em-B
Remeritized gelatin 41.2g and NaCl, 18.5
g was added. After adjusting the pH to 7.2, dimethyl alcohol
Minborane, 8 mg was added. AgNO_Three26g
Double jet of 203mL aqueous solution and KBr aqueous solution
Add so that the final flow rate is 3.8 times the initial flow rate.
It was. At this time, the silver potential is -30 with respect to the saturated calomel electrode.
It was kept at mV. AgNO_ThreeAn aqueous solution containing 110.2 g
440.6 mL and KBr aqueous solution
Accelerate the flow rate so that the final flow rate is 5.1 times the initial flow rate.
Added over 24 minutes. At this time, in the preparation of Em-A1
The AgI fine grain emulsion used had a silver iodide content of 2.3 m.
Add accelerating the flow rate at the same time so that it becomes ol%
The potential was kept at −20 mV with respect to the saturated calomel electrode.
Add 10.7 mL of 1N potassium thiocyanate aqueous solution
After that, AgNO_Three, 24.1 g of aqueous solution 153.
5mL and KBr aqueous solution 2 minutes 30 seconds by double jet method
Added in between. At this time, the silver potential is kept at 10 mV.
It was. Add KBr aqueous solution to adjust silver potential to -70 mV
did. 5. The above-mentioned AgI fine grain emulsion is converted to KI mass.
4 g was added. Immediately after the addition, AgNO_Three57g
Was added over 45 minutes. This
So that the potential at the end of the addition is -30 mV.
Prepared with aqueous r solution. Wash with water in the same way as Em-A1,
Chemical sensitization. (Em-D) Nuclear form in the preparation of Em-C
AgNO at the time of growth_ThreeThe addition amount was changed to 2.0 times. So
The final AgNO_Three, 57 g of aqueous solution containing 57 g
KBr water so that the potential at the end of the addition of +90 mV
Changed to adjust with solution. Otherwise, with Em-C
Prepared in substantially the same manner. (Em-E) Low molecular weight with a molecular weight of 15000
Gelatin, 0.71 g, KBr, 0.92 g, Em-A
Contains 0.2 g of modified silicone oil used in preparation of 1
Maintain 1200 mL of aqueous solution at 39 ° C and adjust pH to 1.8.
Prepared and stirred vigorously. AgNO_Three, Water containing 0.45g
Duplicate the solution and an aqueous KBr solution containing 1.5 mol% KI
It was added over 17 seconds by the Luget method. At this time, KB
The excess concentration of r was kept constant. Raised to 56 ° C and matured
It was. After fully ripening, 35 μmol of methio per gram
97% phthalation rate with a molecular weight of 100,000 containing nin
20 g of phthalated gelatin was added. pH to 5.9
After adjustment, KBr, 2.9 g was added. AgN
O _Three, 288 mL of aqueous solution containing 28.8 g and KBr aqueous solution
The solution was added over 53 minutes by the double jet method. this
The AgI fine grain emulsion used in the preparation of Em-A1
Simultaneously added so that the silver uride content is 4.1 mol%
And the silver potential is -60 mV to the saturated calomel electrode.
Kept. After adding KBr, 2.5 g, AgN
O_Three, 87.7g containing aqueous solution and KBr aqueous solution
The final flow rate is 1.2 times the initial flow rate by the jet method.
The flow was accelerated to 63 minutes and added over 63 minutes. At this time,
AgI fine grain emulsion having a silver iodide content of 10.5 mol
% At the same time to increase the flow rate and add silver potential
Was kept at -70 mV. Add 1 mg of thiourea dioxide
After that, AgNO_Three, 41.8g in aqueous solution 132m
L and KBr aqueous solution over 25 minutes by double jet method
Added. The potential at the end of the addition is +20 mV
The addition of the aqueous KBr solution was adjusted. Benzenethiosulfone
After adding 2 mg of sodium acid, adjust the pH to 7.3.
Arranged. Add KBr to adjust silver potential to -70 mV
After that, the above AgI fine grain emulsion was converted to 5.7 in terms of KI mass.
3 g was added. Immediately after the addition, AgNO_Three66.
Add 609 mL of aqueous solution containing 4 g over 10 minutes
It was. During the initial 6 minutes of addition, the silver potential was reduced to -70 with an aqueous KBr solution.
It was kept at mV. After washing with water, add gelatin and
The pH was adjusted to 6.5, pAg, 8.2. Compound 1 and
Then, the temperature was raised to 56 ° C. AgI mentioned above
Add 0.0004 mol of fine grain emulsion to 1 mol of silver.
After addition, sensitizing dyes 3 and 4 were added. Thiocyan
Potassium acid, chloroauric acid, sodium thiosulfate, N, N-
Dimethylselenourea was added for optimal chemical sensitization. Conversion
Compounds 3 and 4 were added at the end of sensitization. [0117] [Chemical 8] [0118] [Chemical 9] (Em-F) Nuclear form in the preparation of Em-E
AgNO at the time of growth_ThreeE except that the addition amount was changed to 3.1 times
Prepared in substantially the same manner as m-E. However, Em-E sensitization
The dye was changed to sensitizing dyes 5, 6 and 7. [0120] Embedded image [0121] Embedded image [0122] Embedded image (Em-G) Low molecular weight with a molecular weight of 15000
Gelatin 0.70 g, KBr, 0.9 g, KI, 0.1
75 g, modified silicon oy used in the preparation of Em-A1
1,200 mL of an aqueous solution containing 0.2 g of water is kept at 33 ° C.
The pH was adjusted to 1.8 and stirred vigorously. AgNO_Three,
An aqueous solution containing 1.8 g and K containing 3.2 mol% KI
Add Br aqueous solution over 9 seconds by double jet method
It was. At this time, the excessive concentration of KBr was kept constant. 69 ° C
The temperature was raised to aging. After aging, 35μmo / g
Amino having a molecular weight of 100,000 containing 1 methionine
Trimellitic Gela with Chemical Modification of the Group with Trimellitic Acid
27.8 g of chin was added. The pH was adjusted to 6.3
Later, KBr, 2.9 g was added. AgNO_Three27.
Double 270 mL of aqueous solution containing 58 g and aqueous KBr solution
It was added over 37 minutes by the jet method. At this time, molecular weight
15000 low molecular weight gelatin aqueous solution and AgNO_ThreeWater soluble
The magnetic solution described in JP-A-10-43570
In a separate chamber with a gas coupling induction stirrer
Particle size 0.008μ prepared by mixing immediately before addition at
m AgI fine grain emulsion having a silver iodide content of 4.1 mol
% At the same time and the silver potential is
The voltage was kept at −60 mV with respect to the gold electrode. KBr, 2.6g
After adding AgNO_ThreeAn aqueous solution containing 87.7 g;
Final flow rate of KBr aqueous solution by double jet method is initial flow rate
Accelerate the flow rate so that it is 3.1 times higher than 49 minutes
Added. At this time, A prepared by mixing immediately before the above-mentioned addition
The gI fine grain emulsion has a silver iodide content of 7.9 mol%.
The flow rate is accelerated at the same time and the silver potential is -70 mV
Kept. After adding 1 mg of thiourea dioxide, AgN
O_Three, 41.8 g of aqueous solution 132 mL and KBr aqueous solution
The liquid was added over 20 minutes by the double jet method. Addition
Of the aqueous KBr solution so that the potential at the end is +20 mV.
The addition was adjusted. Raise the temperature to 78 ° C and adjust the pH to 9.1
After that, KBr was added to bring the potential to −60 mV. E
The KI mass of the AgI fine grain emulsion used in the preparation of m-A1
5.73 g was added in terms of conversion. Immediately after the addition, AgN
O_Three, 321 mL of an aqueous solution containing 66.4 g
Added. For the first 2 minutes of addition, use a KBr aqueous solution with silver potential.
Was kept at -60 mV. Wash with water in the same way as Em-F,
Chemical sensitization. (Em-H) Ion-exchanged molecular weight of 100
000 gelatin 17.8 g, KBr, 6.2 g, K
I, Keeping aqueous solution containing 0.46g at 45 ° C, stirring vigorously
did. AgNO_Three, 11.85 g of aqueous solution and KBr
An aqueous solution containing 3.8 g in 47 seconds by the double jet method
Added over. Ion-exchanged molecular weight after heating to 63 ° C
Add 24.1g of 100000 gelatin and ripen
It was. After fully aging, AgNO_Three, Including 133.4g
Final flow rate of aqueous solution and KBr aqueous solution by double jet method
Add over 20 minutes to 2.6 times the initial flow rate
did. At this time, the silver potential is +4 with respect to the saturated calomel electrode.
It was kept at 0 mV. 10 minutes after the start of addition₂IrCl₆
0.1 mg of was added. After adding 7 g of NaCl, A
gNO_ThreeAn aqueous solution containing 45.6 g and KBr aqueous solution
It was added over 12 minutes by the Luget method. At this time, silver
The potential was kept at +90 mV. Also 6 minutes after the start of addition
Add 100 mL of an aqueous solution containing 29 mg of yellow blood salt
It was. Preparation of Em-A1 after addition of 14.4 g of KBr
6.3 g in terms of KI mass of the AgI fine grain emulsion used in
Added. Immediately after the addition, AgNO_Three, 42.7g
11 and an aqueous KBr solution containing 11
Added over a minute. At this time, the silver potential is kept at +90 mV.
It was. It was washed with water in the same manner as Em-F and chemically sensitized. (Em-I) Nuclear form in the preparation of Em-H
The temperature was adjusted in the same way except that the temperature during the formation was changed to 38 ° C.
Made. (Em-J) Molecular weight of 97% phthalation rate
00000 phthalated gelatin, 0.38 g, KBr,
Keep 1200 mL of an aqueous solution containing 0.99 g at 60 ° C.
The pH was adjusted to 2 and stirred vigorously. AgNO_Three1.9
An aqueous solution containing 6 g and KBr, 1.97 g, KI, 0.1
72 g of aqueous solution containing 72 g was transferred for 30 seconds by the double jet method.
Added. After ripening, 35 μmol of meg / g
Thionine-containing amino group having a molecular weight of 100,000
Trimellited gelatin chemically modified with Limellitic acid 1
2.8 g was added. After adjusting the pH to 5.9, KB
r, 2.99 g, NaCl 6.2 g were added. AgN
O_Three, 27.3g containing aqueous solution 60.7mL and KBr water
The solution was added over 35 minutes by the double jet method. This
At -30 mV with respect to the saturated calomel electrode
Kept. AgNO_Three, 65.6 g of aqueous solution and KBr
1. The final flow rate of the aqueous solution by the double jet method is the initial flow rate.
Accelerate the flow rate to 1x and add over 37 minutes
It was. At this time, the AgI fine particles used in the preparation of Em-A1
The emulsion was adjusted so that the silver iodide content was 6.5 mol%.
Sometimes the flow rate is accelerated and added, and the silver potential is kept at -30 mV.
It was. After adding 1.5 mg of thiourea dioxide, Ag
NO_Three, 41.8 g of aqueous solution 132 mL and KBr water
The solution was added over 13 minutes by the double jet method. Attendant
KBr water so that the silver potential at the end of heating is +40 mV
The addition of liquid was adjusted. Sodium benzenethiosulfonate
2 mg, and then add KBr to reduce the silver potential.
Adjusted to 100 mV. The above AgI fine grain emulsion is changed to KI.
6.2 g was added in terms of mass. Immediately after the addition, Ag
NO_Three, 88.5g of aqueous solution 300mL in 8 minutes
Added over. The potential at the end of the addition will be + 60mV
It adjusted by addition of KBr aqueous solution. Zera after washing with water
Add tin and adjust to pH 6.5, pAg, 8.2 at 40 ° C.
Arranged. After adding compounds 1 and 2, the temperature was raised to 61 ° C
did. After adding sensitizing dyes 8, 9, 10 and 11,
K₂IrCl₆, Potassium thiocyanate, chloroauric acid, thio
Sodium sulfate and N, N-dimethylselenourea added
The chemical sensitization was optimal. At the end of chemical sensitization, compound 3 and
4 was added. [0127] Embedded image [0128] Embedded image [0129] Embedded image [0130] Embedded image (Em-K) Low molecular weight with a molecular weight of 15000
Aqueous solution 12 containing 4.9 g of gelatin and 5.3 g of KBr
00 mL was kept at 60 ° C. and stirred vigorously. AgNO_Three,
27 mL of aqueous solution containing 8.75 g and KBr, 6.45 g
Double-jet method with 36 mL of aqueous solution containing
Added at. After heating to 77 ° C, AgNO_Three6.9
21 mL of an aqueous solution containing g was added over 2.5 minutes.
NH_FourNO_Three, 26g, 1N, NaOH, 56mL in order
Next, after adding, it was aged. After completion of aging, the pH is adjusted to 4.8
Prepared. AgNO_Three, 141 g of aqueous solution containing 141 g
Dub 458mL of aqueous solution containing 102.6g of L and KBr
The final flow rate is 4 times the initial flow rate by Luget method.
Added. After dropping to 55 ° C, AgNO_Three7.1g
Aqueous solution containing 240 mL and 6.46 g of KI
Was added over 5 minutes by the double jet method. KBr
After adding 7.1 g, sodium benzenethiosulfonate
4mg and K₂IrCl₆, 0.05 mg was added. A
gNO_Three, 177 mL of aqueous solution containing 57.2 g and KB
r, 223 mL of aqueous solution containing 40.2 g passed over 8 minutes
It was added by the double jet method. Same as Em-J
Washed with water and chemically sensitized. (Em-L) Nuclei form in the preparation of Em-K
Except for changing the temperature at the time of formation to 42 ° C, it is almost the same.
Prepared. (Em-M, N, O) Em-H or Em
Prepared in substantially the same manner as -I. However, chemical sensitization is Em-
The method was almost the same as J. (Em-P) For Em-J
Change the sensitizing dye to 5, 6 and 7 to maximize chemical sensitization.
Proceed appropriately to obtain Em-P. The halogene thus obtained
Characteristics of silver halide emulsions Em-A1 to A7 and BP
(Table 1). [0134] [Table 1]1) Support The support used in this example was prepared by the following method.
It was. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P.I. 3
26 (Ciba-Geigy Ciba-Geigy) 2 quality
After drying the part and melting at 300 ° C,
Extrude and stretch 3.3 times at 140 ° C, then
The film is stretched 3.3 times at 130 ° C, and then 250 ° C
PEN (polyethylene with a thickness of 90 μm was fixed by heat for 6 seconds.
Nnaphthalate) film was obtained. This PEN film
Blue dye, magenta dye and yellow dye on film
(Public technique: I-1, described in public technical number 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
An appropriate amount of 5) was added. Furthermore, stainless steel with a diameter of 20 cm
Wrapped around a loess core and heat history at 110 ° C for 48 hours
To provide a support that is difficult to curl. 2) Application of undercoat layer The above support has corona discharge treatment and UV discharge treatment on both sides.
Then, after further glow discharge treatment,
Latin 0.1g / m²Sodium α-sulfodi-2-
Ethylhexyl succinate 0.01g / m², Salici
Luric acid 0.04 g / m², P-chlorophenol 0.2g
/ M², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH
₂0.012 g / m², Polyamide-epichlorohydrin
Polycondensate 0.02 g / m²Apply a primer solution (10c
c / m², Bar coater used), hot surface when stretching undercoat
Provided on the side. Drying was carried out at 115 ° C. for 6 minutes (drying zone
All rollers and conveyors are 115 ° C.
) 3) Coating of back layer The following set as a back layer on one side of the support after undercoating
An antistatic layer, a magnetic recording layer, and a sliding layer were coated. 3-1) Application of antistatic layer Tin oxide-antimony oxide composite with an average particle size of 0.005 μm
The specific resistance of the compound is a dispersion of fine powder of 5 Ω · cm (secondary
Aggregated particle diameter of about 0.08 μm) is 0.2 g / m², Gelatin
0.05g / m², (CH₂= CHSO₂CH₂CH₂N
HCO)₂CH₂0.02 g / m², Poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
m²And coated with resorcin. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization 15) oxyethylene-propyloxy
Coated with citrimethoxysilane (15% by mass)
Cobalt-γ-iron oxide (specific surface area 43m²/ G, long axis
0.14 μm, uniaxial 0.03 μm, saturation magnetization 89 Am²
/ Kg, Fe⁺²/ Fe⁺³= 6/94, the surface is aluminum oxide
Treated with 2% by mass of iron oxide with silicon oxide) 0.0
6g / m²Diacetylcellulose 1.2 g / m²(Oxidation
Iron dispersal is carried out with an open kneader and sand mill.
C) as a curing agent₂H_FiveC (CH₂OCONH-C₆H
_Three(CH_Three) NCO)_Three0.3 g / m²As a solvent.
T, methyl ethyl ketone, and cyclohexanone
Apply with a bar coater and have a thickness of 1.2μm
Got. Silica particles (0.3 μm) and 3 as a matting agent
-Poly (degree of polymerization 15) oxyethylene-propyloxy
A coating coated with trimethoxysilane (15% by mass)
10mg each of aluminum oxide (0.15μm) of abrasive
/ M²It added so that it might become. Drying at 115 ° C for 6 minutes
(All the rollers and conveyors in the drying zone are 11
5 ° C). Magnetic recording with X-light (blue filter)
Layer D^BThe increase in color density is about 0.1, and the magnetic recording layer
The saturation magnetization moment is 4.2 Am²/ Kg, coercive force 7.
3 × 10^FourA / m, the squareness ratio was 65%. 3-3) Preparation of sliding layer Diacetylcellulose (25mg / m²), C₆H₁₃CH
(OH) C_TenH₂₀COOC₄₀H₈₁(Compound a, 6 mg /
m²) / C₅₀H₁₀₁O (CH₂CH₂O)₁₆H (compound b,
9mg / m²) The mixture was applied. This mixture
Xylene / propylene monomethyl ether (1 /
1) Propylene monomethyl melted at 105 ° C in room temperature
After pouring and dispersing in ruether (10 times amount),
After making dispersion (average particle size 0.01μm) in seton
Added. Silica particles (0.3 μm) as a matting agent
Abrasive 3-poly (degree of polymerization 15) oxyethylene propylene
Coated with ruoxytrimethoxysilane (15% by mass)
15 mg / m each of aluminum oxide (0.15 μm)
²It added so that it might become. Drying was performed at 115 ° C. for 6 minutes.
(All the rollers and conveyors in the drying zone are 115
° C). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ step).
Nres hard ball, load 100g, speed 6cm / min), static
Coefficient of friction 0.07 (clip method), emulsion surface described later
The coefficient of dynamic friction of the sliding layer was also excellent at 0.12.
It was. 4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, the following composition
Sample 1 which is a color negative photosensitive material
01-121 were created. That is, in the 14th layer
(Salt) As silver iodobromide emulsion, emulsions Em-A1 to Em1
By using Em-A7, each of the samples 101 to 10
7 was created. Moreover, the hardening agent H-1 added to the 16th layer
Samples 107 to 121 were changed in the amount of addition of (Table 2).
It was created. [Table 2] (Composition of photosensitive layer) Main materials used for each layer
Are classified as follows:     ExC: Cyan coupler UV: UV absorber     ExM: Magenta coupler HBS: High boiling point organic solvent     ExY: Yellow coupler H: Gelatin hardener (hardener) (Specific compounds are described below.
The chemical formula is listed behind) The number corresponding to each component is g / m²Application amount expressed in units
For silver halide, the coating amount in terms of silver is shown.
The [0142]   First layer (first antihalation layer)     Black colloidal silver Silver 0.155     0.07 μm surface fogging AgBrI (2) Silver 0.01     Gelatin 0.87     ExC-1 0.002     ExC-3 0.002     Cpd-2 0.001     HBS-1 0.004     S-37 0.002 [0143]   Second layer (second antihalation layer)     Black colloidal silver Silver 0.066     Gelatin 0.407     ExM-1 0.050     ExF-1 2.0 × 10^-3     HBS-1 0.074     Solid disperse dye ExF-2 0.015     Solid disperse dye ExF-3 0.020 [0144]   Third layer (intermediate layer)     0.07 μm AgBrI (2) 0.020     ExC-2 0.022     Cpd-1 0.05     HBS-1 0.05     Polyethyl acrylate latex 0.085     Gelatin 0.294 [0145]   4th layer (low sensitivity red sensitive emulsion layer)     Silver iodobromide emulsion M Silver 0.065     Silver iodobromide emulsion N Silver 0.100     Silver iodobromide emulsion O Silver 0.158     ExC-1 0.109     ExC-3 0.044     ExC-4 0.072     ExC-5 0.011     ExC-6 0.003     ExC-8 0.03     Cpd-2 0.025     Cpd-4 0.025     HBS-1 0.17     Gelatin 0.80 [0146]   5th layer (medium sensitivity red emulsion layer)     Silver iodobromide emulsion K Silver 0.21     Silver iodobromide emulsion L Silver 0.62     ExC-1 0.14     ExC-2 0.026     ExC-3 0.020     ExC-4 0.12     ExC-5 0.016     ExC-6 0.007     ExC-8 0.03     Cpd-2 0.036     Cpd-4 0.028     HBS-1 0.16     Gelatin 1.18 [0147]   6th layer (high-sensitivity red-sensitive emulsion layer)     Silver iodobromide emulsion J Silver 1.67     ExC-1 0.18     ExC-3 0.07     ExC-6 0.047     Cpd-2 0.046     Cpd-4 0.077     HBS-1 0.37     Gelatin 2.12 [0148]   7th layer (intermediate layer)     Cpd-1 0.089     Solid disperse dye ExF-4 0.030     HBS-1 0.050     Polyethyl acrylate latex 0.83     Gelatin 0.84 [0149]   Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))     Silver iodobromide emulsion E Silver 0.560     Cpd-4 0.030     ExM-2 0.096     ExM-3 0.028     ExY-1 0.031     ExG-1 0.006     HBS-1 0.085     HBS-3 0.003     Gelatin 0.58 [0150]   9th layer (low sensitivity green emulsion layer)     Silver iodobromide emulsion G Silver 0.39     Silver iodobromide emulsion H Silver 0.28     Silver iodobromide emulsion I Silver 0.35     ExM-2 0.36     ExM-3 0.045     ExG-1 0.005     HBS-1 0.28     HBS-2 0.01     S-2 0.27     Gelatin 1.39 [0151]   10th layer (medium sensitive green sensitive emulsion layer)     Silver iodobromide emulsion F Silver 0.20     Silver iodobromide emulsion G Silver 0.25     ExC-6 0.009     ExC-8 0.01     ExM-2 0.031     ExM-3 0.029     ExY-1 0.006     ExM-4 0.028     ExG-1 0.005     HBS-1 0.064     HBS-2 2.1 × 10^-3     Gelatin 0.44 [0152]   11th layer (high sensitivity green emulsion layer)     Silver iodobromide emulsion P Silver 1.200     ExC-6 0.004     ExC-8 0.01     ExM-1 0.016     ExM-3 0.036     ExM-4 0.020     ExM-5 0.004     ExY-5 0.008     ExM-2 0.013     Cpd-4 0.007     HBS-1 0.18     Polyethyl acrylate latex 0.099     Gelatin 1.11 [0153]   12th layer (yellow filter layer)     Yellow colloidal silver Silver 0.047     Cpd-1 0.16     Solid disperse dye ExF-5 0.010     Solid disperse dye ExF-6 0.010     HBS-1 0.082     Gelatin 1.057 [0154]   13th layer (low sensitivity blue-sensitive emulsion layer)     Silver iodobromide emulsion B Silver 0.18     Silver iodobromide emulsion C Silver 0.20     Silver iodobromide emulsion D Silver 0.07     ExC-1 0.041     ExY-1 0.035     ExY-2 0.71     ExY-3 0.10     ExY-4 0.005     Cpd-2 0.10     Cpd-3 4.0 × 10^-3     HBS-1 0.24     Gelatin 1.41 [0155]   14th layer (high sensitivity blue-sensitive emulsion layer)     (Salt) Silver iodobromide emulsion Em-A1 to Em-A7 Silver 0.75     ExC-1 0.013     ExY-2 0.31     ExY-3 0.05     ExY-6 0.062     Cpd-2 0.075     Cpd-3 1.0 × 10^-3     HBS-1 0.10     Gelatin 0.91 [0156]   15th layer (first protective layer)     0.07 μm AgBrI (2) Silver 0.30     UV-1 0.21     UV-2 0.13     UV-3 0.20     UV-4 0.025     F-11 0.009     F-18 0.005     F-19 0.005     HBS-1 0.12     S-2 5.0 × 10^-2     Gelatin 2.3 [0157]   16th layer (second protective layer)     H-1 (described in Table 2)     B-1 (diameter 1.7 μm) 5.0 × 10^-2     B-2 (diameter 1.7 μm) 0.15     B-3 0.05     S-1 0.20     Gelatin 0.75 Furthermore, preservability, processability, and pressure are appropriately applied to each layer.
Resistance, antifungal and antibacterial, B-4 to B-6, no F-1
F-18 and iron salt, lead salt, gold salt, platinum salt, parajiu
Contains salt, iridium, ruthenium and rhodium salts
Has been. In addition, the silver halide 1 mol
8.5 x 10 per ru^-3Gram, 7.9 x 1 in the 11th layer
0^-3Add gram of calcium with aqueous calcium nitrate solution
A sample was prepared. To further improve antistatic properties
Contains at least one of W-1, W-6, W-7, W-8
In order to improve coatability, less W-2 and W-5
Contains at least one. Preparation of Dispersion of Organic Solid Disperse Dye
xF-3 was dispersed by the following method. That is, 21.7 mL of water
And 5% aqueous solution of p-octylphenoxyethoxyate
3 mL of sodium xietan sulfonate and 5% aqueous solution
p-octylphenoxy polyoxyethylene ether
(Polymerization degree 10) 0.5g to a 700mL pot mill
And 5.0 g of dye ExF-3 and zirconium oxide
(1mm diameter) 500mL is added and the contents are 2 o'clock
Dispersed. For this dispersion, the BO-type vibration bow manufactured by Chuo Koki
Lumil was used. After dispersion, the contents are removed and 12.5
Add to 8 g of aqueous gelatin solution and filter out beads.
A gelatin dispersion of the dye was obtained. Average particle size of dye fine particles
The diameter was 0.44 μm. Similarly, a solid dispersion of ExF-4 was obtained.
It was. The average particle diameter of the dye fine particles was 0.24 μm. E
xF-2 is European Patent Application Publication (EP) No. 549,489.
Microprecipitation described in Example 1 of the A specification (Microp
dispersion).
The average particle size was 0.06 μm. ExF-6 solid content
The dust was dispersed by the following method. ExF- containing 18% water
6 wet cake 2800g, 4000g water and W
376 g of a 3% solution of -2 was added, and the mixture was stirred.
A slurry having a concentration of 32% was obtained. Next, Imex Corporation
Ultraviscomil (UVM-2) made with an average particle size of 0.5
Filled with 1700 mL of mm zirconia beads,
Through the peripheral speed of about 10m / sec, discharge rate 0.5L / m
In milled for 8 hours. The average particle size was 0.45 μm
It was. The compounds used to form each of the above layers are shown below.
It is. [0161] Embedded image[0162] Embedded image[0163] Embedded image[0164] Embedded image[0165] Embedded image[0166] Embedded image[0167] Embedded image[0168] Embedded image[0169] Embedded image[0170] Embedded image [0171] Embedded image[0172] Embedded image[0173] Embedded image[0174] Embedded image[0175] Embedded image [0176] Embedded image The sample evaluation method is as follows. FUJIFILM
Gelatin filter SC-39 (cut-off wave)
Long wavelength light transmission filter with a length of 390 nm) and continuous
1/100 second exposure through the wedge. Development is Fuji Photo
Using an automatic processor FP-360B manufactured by Film Co., Ltd.
More went. In addition, the overflow solution of the bleaching bath flows to the back bath.
Instead, it was modified so that everything was discharged into the waste liquid tank. This
FP-360B is the Japan Society of Invention Disclosure Technique 94-4992
Is mounted. The processing steps and the processing liquid composition are shown below.   (Processing process)     Process Processing time Processing temperature Replenishment amount * Tank capacity   Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L   Whitening 50 seconds 38.0 ℃ 5 mL 5L   Fixing (1) 50 seconds 38.0 ℃ -5L   Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L   Washing with water 30 seconds 38.0 ℃ 17 mL 3L   Stable (1) 20 seconds 38.0 ℃ -3L   Stable (2) 20 seconds 38.0 ℃ 15 mL 3L   Dry 1 min 30 sec 60.0 ° C   * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1) Stabilizer and fixer are countercurrent from (2) to (1)
In this case, all the overflow water of the washing water is led to the fixing bath (2).
I entered. The amount of developer brought into the bleaching process, bleach solution
To the fixing process and to the washing process of the fixing solution
The amount brought in is 35mm per photosensitive material and 1.1m wide.
2.5 mL, 2.0 mL, and 2.0 mL. Ma
The crossover time is 6 seconds.
The time is included in the processing time of the previous process. Open the above processor
Mouth area is 100cm with color developer²120c with bleach
m²Other processing solutions are about 100cm²Met. The composition of the treatment liquid is shown below.   (Color developer) Tank solution (g) Replenisher (g)   Diethylenetriaminepentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3mg −   4-hydroxy-6-methyl-1,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-Methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18 [0180]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-diaminopropanetetraacetic acid second     Iron ammonium monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia] 4.6 4.0 (Fixing (1) Tank liquid) The above bleach tank liquid
And 5 to 95 (volume ratio) of the following fixing tank solution (pH)
6.8) [0182]   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240 mL 720 mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45 (Washing water) Tap water is changed to H-type strongly acidic cation exchange
Replacement resin (Rum & Haas Amberlite IR-
120B) and OH type strongly basic anion exchange resin (same as above)
To a mixed bed column packed with mberlite IR-400)
Pass water and adjust calcium and magnesium ion concentration to 3m
g / L or less, followed by isocyanuric dichloride
Thorium 20mg / L and sodium sulfate 150mg / L
Was added. The pH of this solution is in the range of 6.5 to 7.5.
It was. [0184]   (Stabilizer) Tank fluid and replenisher common (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average polymerization degree 10)   1,2-Benzisothiazoline-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   Add water and add 1.0L   pH 8.5 The samples 101 to 121 were subjected to the above treatment.
did. Blue and green filters for processed samples
-Photograph by measuring the density with red filter
Performance evaluation was performed. In addition, for samples 101-121
The swelling rate was measured. The results obtained are shown in (Table 3).
The [0186] [Table 3] From Table 3, the sample of the present invention is compared to the comparative sample.
High sensitivity is achieved in a balanced manner for each of the blue, green and red layers.
ing. [0188] The color photographic light-sensitive material of the present invention is blue,
The green and red photosensitive layers can achieve high sensitivity in a balanced manner.

Claims (1)

1. A unit blue-sensitive silver halide emulsion layer, a unit green-sensitive silver halide emulsion layer each comprising two or more color-sensitive layers having different sensitivities on a support, and A silver halide color light-sensitive material having a unit red-sensitive silver halide emulsion layer, wherein the projected area of all silver halide grains in at least one of the emulsion layers contained in each unit color-sensitive layer in the light-sensitive material The grains occupying 50% or more are composed of tabular silver halide grains having an equivalent circle diameter of 3.5 μm or more with the (111) plane as the main plane, and the water swelling speed T of the photosensitive material is 1/45 [ sec ^-1 ] or more, a silver halide color photographic light-sensitive material characterized by the above.