JPS62205344A - Silver halide color photographic sensitive mateial - Google Patents

Abstract

PURPOSE:To enhance sharpness by incorporating a means for forming an unsharp positive image in combination with at least one of emulsion layers containing a compound to be allowed to release a fogging agent and/or a layer different from it. CONSTITUTION:At least one of the silver halide emulsion layers contains the compound to be allowed to release the fogging agent, a development accelerator, or one of their precursors by the coupling reaction with the oxidation product of a developing agent, preferably, in an amount of 10-10<-4>mol of silver halide. As the means for forming an unsharp positive image in combination with said layer and/or the other different layer, preferably, a compound for forming an unsharp positive image in combination with the silver halide emulsion layer for forming a color negative image, containing a diffusion resistant coupler is enumerated, thus permitting the obtained photosensitive material to be high in sensitivity and improved in sharpness.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a negative-working silver halide photographic material. More specifically, the present invention relates to a negative-working silver halide photographic material having high sensitivity and high sharpness. [Background of the Invention] In recent years, two major trends can be seen in silver halide photographic materials, particularly in photographic materials. One is IS
One is higher sensitivity, as typified by O1600 film, and the other is higher image quality, which corresponds to smaller film sizes. Regarding the former, various methods have been studied, including increasing the size of silver halide grains, increasing coupler activation, and accelerating development. For increasing the size of silver halide, υ, C, Far
nellw, 1.8. Chanter, J., Pb.
As reported in Otogr, Sci., 9.75 (1961), there is already a tendency for the sensitivity to reach a plateau, and even if the size is increased, it cannot be expected that the sensitivity will increase much. Furthermore, increasing the size of silver halide grains is accompanied by severe co-location, such as deterioration of graininess. Many studies have been conducted on increasing the activation of couplers, but they do not contribute enough to sensitivity and have the disadvantage of worsening graininess. The addition of various development accelerators, mainly hydrazine compounds, to the emulsion layer or developer has been considered, but these methods are often accompanied by an increase in JQ and deterioration of graininess, and are not practical. ,: Improvement - As a first step, a caplase agent is released into ImenoY X to stir up undeveloped silver halide grains near the silver halide grains where development has started, thereby initiating development. The method is JP-A-57-150845.59-504.
:(9,59-157638,59-t7o84o,
59-172640.60-37556.60-154
245.60-156059.60-128429.6
(1128430, 60-128431, 60-153
No. 039, 60-191241, 61-15142. However, fogging agent releasing compounds are known to have the serious drawback of deteriorating sharpness. Conventionally, in order to improve sharpness, studies have been made from both optical and developing effects. From the optical point of view, monodisperse silver lodenide grains (A) have attracted attention from the viewpoint of irradiation transmittance, and studies have been made to make them thinner from the viewpoint of light scattering paths.
(For example, Journal of tl+e 0pti-
cal 5ociety of America 58
(9)y 1245-1256 (+968),
PI+otographic 5science a
nd Engineering 1 store (3), 181
~+91 (1972) etc.). However, the effect of -'+L dispersible silver halide f is insufficient, and in thinning the film, mere placement of pine goo may cause pressure capri and perspiration (when the photosensitive material is placed in high temperature and high humidity). This causes problems such as oily components (bleeding), and reducing the amount of couplers and high-boiling solvents causes a decrease in color density. In particular, it is not effective as a means for improving the deterioration in sharpness caused by the compound released by fogging. In addition, from the perspective of development effect, the inhibitor is released during development and Ed
It is known to use IR couplers to enhance the ge effect. 11 (When using a coupler, if the amount used is small, the effect will be insufficient; if the amount 14 used is too large, it will deteriorate the storage stability of the photosensitive material or desensitize it, and the inhibitory components liberated during development will i) Degraded the activity of the developer.
cause problems. [Object of the Invention] An object of the present invention is to provide a silver halide photographic material having high sensitivity and improved sharpness. [Structure of the Invention] The object of the present invention is to provide a silver lodenide photographic material having at least one silver halide emulsion layer on the support 1-, in which at least one layer contains a fogging agent, a development accelerator, or these. A compound that releases a precursor of the developing agent by a coupling reaction with an oxidized developing agent, and includes means for forming an unsharp positive image in combination with a layer containing the compound and/or a layer different from the layer. This was achieved in a negative-type silver halide photographic material characterized by the following. An unexpected effect was obtained in that the sharpness-enhancing effect of the unsherbed topoimage-forming compound was synergistically enhanced in the presence of the fogging agent-releasing compound. [Specific Structure of the Invention] A compound that releases a fogging agent or a development accelerator used in the present invention, or a precursor thereof through a coupling reaction with an oxidized form of a developing agent (hereinafter referred to as the "anti-fogging agent releasing agent of the present invention") The compound) is preferably represented by the following general formula CI) or (It). CII] Coup (TIME)n,
11^ In the formula, Coup is a coupler residue that can cause a coupling reaction with the oxidized product of the aromatic 1JS primary amine developer, and Tl14E is a C
After being released from oup, there is a timing group that further releases D8, and nl is 0 or 1. D^
When 1 is 0, it is a group that can be separated from Coup in the coupling reaction, and when nl is 1, it is a group that can be released from TIME, and has adsorption to silver halide grains. , is a group having a substantially lr-rotating effect on silver halide grains, and Z is Cou
p - (TIME) Represents a group of nonmetallic atoms necessary to form a ring structure together with nl. Here, the term "group having a substantial fogging effect" refers to a group (compound) that produces a measurable fog when developed in the presence of the compound. Z is a nonmetallic atom Jf necessary to form a ring structure (preferably 5 to 7 shell rings) with a part of Coup-TIME
fヲ表waL, alkylene, alkenylene, phenylene,
It is composed of a group selected from divalent groups such as imino, -0-1-S-, carbonyl, and sulfonyl. The following coupler residues are represented by Coup in Table 1). Examples of cyan coupler residues include 7E/- coupler and naphthol coupler. Examples of magenta couplers include 5-pyrazolone couplers, vilazolobenlimigzole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and indacylon couplers. Yellow coupler residues include benzoylacetanilide couplers, pivaloylacetanilide couplers, maloncyanilide couplers, and the like. Colorless coupler residues include open-chain or cyclic active methylene compounds (e.g. indanone, cyclopentanone, malonic acid noester, imidazolinone,
oxazolidine, thiazolinone, etc.). Further, among the coupler residues represented by Cou p, those preferably used in the present invention can be represented by the general formula %, [l\], [X], or [XI]. [111) 1(,9 In the formula, R18 represents an acylamido group, anilino group, or ureido group, and is substituted with a halogen atom, alkyl group, alkoxy group, or cyano group. [IYI (V) In the formula 7, R20 represents a halogen atom, an acylamido group, or an aliphatic residue, R21 and R2□ each represent an aliphatic residue,
Represents an aromatic residue or a heterocyclic residue. Also, one of r(2+ and R2□ may be a hydrogen atom. a is an integer of 1 to 4, b is an integer of 0 to 3, and C is an integer of 0 to 5.
represents an integer. [■] [■] In the formula, R2 represents a tertiary alkyl group or an aromatic residue, and R2 represents a hydrogen atom, a halogen atom, or an alkoxy group. R2S represents an acylamido group, an aliphatic residue, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom or a sulfonamide group. (IYI l?-17□6 in the formula is an aliphatic residue, an alkoxy group, a mercapto group, an alkylthio group, an acylamido group, an alkoxycarbonyl group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxysulfonyl group, an aryloxysulfonyl group) , represents an acyl group, a diacylami7 group, an alkylsulfonyl group or an arylsulfonyl group, and R
2° represents a hydrogen atom, a halogen atom, an alkoxy group, an acyl group, a nitro group, an alkylsulfonyl group, or an alkylsulfonyl group;
X) R? . In the formula, R2a represents an aliphatic residue or an aromatic residue, and
represents an oxygen atom, a sulfur atom or a nitrogen atom. (XI) R2gCR:+. ■ R31, 1, 2, and R33 each represent a hydrogen atom, an aliphatic residue, an aromatic residue, or a heterocycle17, W is necessary to form a 5- to 6-shell ring with a nitrogen atom; represents a group of nonmetallic atoms. R29 and R3° may form a ring with a necessary nonmetallic atom group. As a timing group represented by TIME, U.S. Patent 4
, 248,962, JP-A No. 57-56837, etc., which leaves Cou p by a coupling reaction and then leaves D^ by an intramolecular substitution reaction, British Patent No. 2,072,363Δ No., Japanese Patent Publication No. 57-1542
No. 34, No. 57-188035, etc., which leave D^ by electron transfer via a conjugated system, JP-A-57
Examples include those which are coupling components capable of releasing D^ through a coupling reaction with an oxidized product of an aromatic primary amine developer, such as No. 111536. These reactions may occur in one step or in multiple steps. As D^, for example, ^9S (Q)+++1-
A group represented by X s or ^11S in one group
It is a group that has the effects or depictions of and X. Here, AIts represents a group that can be adsorbed to silver halide grains, Q represents a divalent linking group, and X is a reducing group or a group that can form silver sulfide during development,

[n, is
0 or 1. D^ is 8BS (Q)Lmt -
When it is a group represented by X 3, it binds to TIME
The position may be any of 8BS-(Q)m+-X3.
. Of course, D^ is one group and the action and effect of BS and X3 are
Those that also have fruits are also preferably used. Also, ^BS is directly bonded to the carbon atom at the coupling position.
Q or X3 is a coupling reaction.
These are coupling coals if they can be separated by
May be simply bonded. Also, coupling carbon and ^B
What is known as the so-called 2-equivalent leaving group between S
may be present. These groups include alkoxy
groups (e.g. methoxy group), aryloxy groups (e.g.
phenoxy group), alkylthio group (e.g. ethylthio group)
Arylthio group (e.g. phenylthio group), heterocyclic group
xy group (e.g. tetrazolyloxy), heterocyclic thio group
(e.g. pyridylthio) heterocyclic groups (e.g. pyridylthio)
Nyl group, pyrazolyl group, triazolyl group, benzotria
zolyl group, etc.). Others, British patent publication 2,01
1,391 can be used as D^.
Ru. A group capable of adsorption to silver halide represented by ^BS
is a nitrogen heterocycle with a dissociable hydrogen atom.
role, imidazole, pyrazole, triazole, te
torazol, benzimidazole, benzopyrazole,
benzotriazole, uracil, tetraazaindene,
imigzotetrazole, pyrazolotriazole, penta
azaindene, etc.), with at least one nitrogen atom in the ring
Other heteroatoms (oxygen atoms, sulfur atoms, selenium atoms)
4) heterocycles (oxazole, thiazole, thia
Zolin, thiazolidine, thyanazole, benzothiazo
(benzoxazole, etc.), hydrogen with mercapto group
Terocycle (2-mercaptobenzothiazole, 2-mercaptobenzothiazole,
Ptovirimipin, 2-mercaptobenzoxazole,
1-phenyl-5-mercabutotetrazole, etc.), quaternary
Salts (tertiary amines, pyridine, quinoline, benzothiazo
quaternary compounds such as chlorine, benzimidazole, benzoxazole, etc.
salts), thio7er7-ols, alkylthiol M (system
For example, thiourea, dithiocarbamate, thioamide,
rhodanine, thiazolinonethione, thiohyguntoin,
Thiobarbic acid, etc.)
can. The divalent linking group represented by Q in h is normally used.
alkylene, alkenylene, phenylene, naphthylene
-〇-1-S-1-SO-1-SO□-1-N=N
-, carbonylamide, thioamide, sulfonamide,
Selected from ureido, thioureido, heterocycle, etc.
composed of things. The group represented by X3 is a reducing compound 11&l (H
drazine, hydrazide, hydrazone, hydroquinone,
Catechol, p-7 minophenol, p-phenylene
Amine, 1-phenyl-3-pyrazolycyan, enamine
, aldehyde, polyamine, acetylene, aminoborane
, terazolium salt, ethylene bispyridinium salt
quaternary salt carbamic acid, etc.) or silver sulfide during development.
Compounds that form (thioureas, thioamides, dithiocals)
Bamate, Logenine, Thiohyguntoin, Thiazolino
such as cations (those having a -C-N< partial structure, etc.)
). Of the groups represented by X, those that can form silver sulfide during development
Some of the objects themselves become silver halide grains.
It has adsorptive properties for
be able to. DΔ is an adsorption site for silver halide grains (e.g.
Nitrogen atom of benzotriazole, 1-phenyl-5-methane
sulfur atom of lucapotetrazole)
may be combined with Coup, but this is not necessarily the case.
No9 In this case, a hydrogen atom is bonded to the adsorption site.
or adsorption sites with groups that can be hydrolyzed in the developer (
For example, acetyl group, benzoyl group, methanesulfonyl group
) or an IBL releasable group (e.g., 2-7ethyl group)
, 2-methanesulfonylethyl group)
Preferably 1. An example of 80S is shown below. An example of Q is shown below. -C112--CIl, C1h-icI+2--OCI
I2C112--3CH2--1! J- An example of X3 is shown below. 2l− =20= −NIINIICIIO−NlkakuIC0CI+,
-N! lNll5O2C11゜-NIINIICO
C.F. Preferred examples of D^ are shown below. C! ! 2CII□Cll0 Cl+3 -Z/- I Preferred embodiments of the compound represented by the general formula [l], (IT)
Examples are as follows. (F-5) し113 (F 6) NIINIICIIO =31- (F-7) (1'-8) <F-9) (F-11) (F-12) ? 11. (F-13) 9+1. (F-17) (1”-19) ll (F-26) (F'-27) n-c:,,+1.,ococllcooc,,l+1
．． -n薯(!'-28) IlJ (F-29) (P-30) 4O- (F"-31) Shi++. (F-32) (F-33) (F-34) (F 35) (F-36) (F-37) The fogging agent releasing compound of the present invention can be used, for example, in JP-A-57-1
It is synthesized according to the synthetic route described in No. 50845. The fogging agent-releasing product of the present invention is applied to a halogen silver emulsion layer.
This can be done using known methods such as U.S. Pat.
The method described in No. 027 can be used. For example, 7-tar acid alkyl ester (dibutyl 7-tar)
esters, dioctyl phthalate, etc.), phosphate esters (
diphenyl 7mose 7ate, tri-7enyl 7mose 7a
tricresyl 7 male 7 ate, tricresyl 7 male 7 ate, octyl butyl 7
male 7-ate), citric acid esters (e.g. acetyl
tributyl citrate), benzoic acid esters (e.g.
octyl zoate), alkylamides (e.g. diethyl
lufurilamide), fatty acid esters (e.g.
toxyethyl succinate, dioctyl azelate),
trimesic acid esters (e.g. trib trinosinate)
chill), or boiling, α about 30°C to 150°C
Solvents, such as lower acetates such as ethyl acetate and butyl acetate.
Rukyl acetate, 70 ethyl pionate, secondary butyl acetate
alcohol, methyl isobutyl ketone, β-ethoxyethyl
Dissolved in celloacetate, methyl cellosolve acetate, etc.
It is then dispersed into hydrophilic colloids. − High boiling temperature as described in
ξ′! : Mixing Aritsuki solvent and low boiling point organic solvent 1. 'C for
You can stay there. Also, Japanese Patent Publication No. 51-39.853, Japanese Patent Publication No. 5+-59,
The dispersion method using polymers described in No. 943 can also be used.
can be done. The coupler has an acid group such as carboxylic acid or sulfonic acid.
When using woody colloids as an alkaline aqueous solution
introduced inside. In the present invention, the fogging agent releasing compound is 1 mole of silver halide.
to be added in 10 to 1X10-' mol%
is preferable, and more preferably 1 to 1XIO-3 mol%.
preferable. Preferred as a means of forming unsharp positive images
Color negative images containing diffusion-resistant couplers
Unsher combined with a forming silver halide emulsion layer
A positive image forming compound (hereinafter referred to as a positive compound) is
Can be mentioned. One preferred example of a positive compound is a small diffusive one, as mentioned above.
Diffusion-resistant couplers react with oxidized forms of color developing agents.
The main absorption wave of the pigment (hereinafter referred to as coloring pigment) produced by
Colored compounds with major absorption in the long range or during development processing
The compound that changes color to the colored compound is a so-called precursor.
As a result of the reaction with the oxidized form of the developing agent, the color disappears or develops.
Diffusion-resistant dyes with main absorption in the main absorption wavelength range of the element
The generated compound (hereinafter referred to as a small diffusible positive compound)
It is. Another preferable example of a positive compound is a diffusion-resistant compound.
Yes, it has a main absorption in the main absorption wavelength range of the coloring dye.
A color compound or a compound that changes color during development processing
A decolorizing product that is produced as a result of a reaction with an oxidized form of a developing agent.
(hereinafter referred to as a diffusion-resistant positive compound).
. The small diffusible Bonn compound will be explained in detail. Low diffusivity is a phenomenon that occurs in the drawing process using photographic materials.
Diffusion resistance used in combination, especially in the development process.
Diffuses more than the coupler, but is added after the processing step
At least 30 iut% of the amount remains in the photographic material.
say what you are doing. Also, as for the degree of discoloration, the change in maximum absorption wavelength is 10 nI.
It is preferably 11 or more -1-. Dark discoloration mechanism and
In this case, the color tone changes due to the hydrolysis of the botanic compound.
Preferred examples include those that change. Also, decoloring means not producing colored compounds or not producing colored compounds.
Colored compounds flow out of the photographic material during the development process.
At the end of the drawing process, unsharp points can be
colored compounds in photographic materials to the extent that they impair image formation.
This means that it does not remain. Such a color erasable non-diffusible Bonn compound is a color developing agent and a supernatant.
A color image is produced by reaction with a diffusion-resistant coupler.
In this region, it reacts with the oxidized form of the developing agent and erases the color. Also, resistance
Unreacted in areas where no color image is produced by the diffusive coupler
Or it remains in a discolored state. As a result, 1iit expansion
Color images with dispersive couplers and colorless non-diffusible positive compounds
A color image with an inverse relationship to that of , i.e., the former forms an image
On the other hand, the latter forms a positive image. deer
Also, a small diffusivity positive compound has a small diffusivity.
, an unsharp image, i.e. an unsharp positive image
will be formed. Next, as a result of the reaction with the oxidized form of the developing agent, the main absorption of the coloring dye occurs.
Produces a diffusion-resistant dye with main absorption in the wavelength range
type of small diffusible positive compound, i.e. a diffusion-resistant dye-forming non-containing compound.
Let's talk about diffusible positive compounds. Diffusion-resistant dye-forming non-diffusible positive compounds are
Unreacted or discolored in areas where color images do not occur
do. The result is a color image with diffusion-resistant couplers and an unreflected
A color image with an inverse relationship to a small diffusive positive compound that has changed color or changed color.
, that is, if the former is a negative image, the latter is a positive image.
will be accomplished. Moreover, small diffusive positive compounds have small diffusivity.
Unsharp images, i.e.
This results in the formation of an unsharp positive image. Diffusion-resistant dye-forming non-diffusible positive compounds are
In addition to forming unsharp positive images, the developing agent
Due to the reaction with the oxidized form of
Produces diffusion-resistant dyes with barrel absorption. This anti-diffusion
The coloring dye is a diffusion-resistant coupler and an acid color developing agent.
Together with the diffusion-resistant pigment produced by the reaction with the compound,
Form a color image. This diffusion-resistant dye-forming small-diffusible Bonn compound is as described above.
It consists of a dark, unsharp blurred image and -4 diffusive dye.
Produces both negative images. Therefore, both images overlap,
From a macroscopic perspective, it may appear that no concentration change occurs.
However, the edge part (the boundary part where the intensity of the irradiated light changes)
Next, we will examine the diffusion properties of the positive compound and the produced diffusion-resistant dye.
The difference causes microscopic concentration changes (edge effect).
It is effective as an unsharp positive image forming means.
It is. Examples of decolorizing non-diffusible borosilicate compounds include the following general
Examples include compounds represented by formula [1]. General formula (1) A-Link B In the formula, A reacts with the oxidized developing agent to form the Link-8 portion.
”Organic residues that can be released depending on the amount of oxidized developer
, L i n k is a group that connects A and B, and 13 is a group that connects A and B.
Represents an organic residue. Moreover, the compound represented by the general formula [l] is not used during the development process.
A colored or color-changing compound that diffuses through a photographic material.
Yes, after the reaction, the production caused by A and 1.1nk-B
If the product is a colored compound, the product can be photographed after the reaction.
Hydrophilic or lipophilic roses flow out of the yarn from the inside of the yarn.
It is accompanied by a substituent that takes a certain stance. As A in general formula [1], for example, a color developing agent
A colored or colorless product is produced by coupling reaction with the oxidant of
cross with the residue of the coupler or the oxidized form of the developing agent that results in
Examples include components that undergo oxidation reactions. Specific examples of melody include phenols, naphthos, etc.
ols, 5-pyrazolones, pyrazolotriazoles,
Pyrazolobenzimidazoles, ingzolones, reeds
Ruase I anilides, ItCOC! +3 (R is an example
alkyl, aryl, heterocyclic group) U
N0II
N-NIIH'<7. For example, 5 to 8 shellfish are saturated or
is 1: a group of atoms that completes a saturated 1ift ring or heterocycle
In this case, the residue 1 (' indicates the aryl residue J) is listed.
It will be done. As an example of the latter 11 bodies, for example, after being oxidized, alkali
B-SO2 old 1e as 1.1nk-B by re-cleavage
7 ethanols, naphthols, and 7 ethanols to be released,
Residues of indoles and hydroquinones, after oxidation
, undergoes an intramolecular ring-closing reaction and becomes B5-5 as 1ink-B.
Phenols that release O2e (For details, see US patent @
No. 3,443,939, No. 3,443.94f1,
It is described in No. 3.443.941. ) residues are
Can be mentioned. If r=■1, then 1, for example -N=N-, -0-. -s-, -Nll-8O2-, -3Q2-NII-, -
N,, - 辷. -C11-, -CI-, and the like. [< Here, -Ne is a nitrogen-containing heterocyclic residue, for example, amber
imidoyl acid, imidoyl heptalate, pyridoyl, imidoyl
dazolyl imigzolonil, benrayimigzolyl, hig
Ntoyl, Thiohigntoyl, Triazolyl, Penztoyl
Riazolyl, ura=51-zolyl, 2,4-dioxyoxazolyl, 2,4-one'
Oxothiazolyl, cyanoazolyl, tetrazolyl
and so on. In addition, each R is an atom that may have a substituent.
These include Lukil and Aryl. ``As 3, L i n k is -N=N-1-011
In the case of chromophores such as -, for example, aryl groups or hetero
Even if it is a cyclic group, preferably an organic residue having an auxochrome
It may also be a dye residue. Also, L in k is a chromophore
If not, dyes (e.g. azo, anthraquinone,
azomethine, indophenol, indoaniline, etc.)
It is preferable that it is a group. With this configuration, the general formula (1
) is the B moiety or A-Link
n may be a colored or color-changing compound as a whole. The compound represented by the general formula [1] slightly spreads during the development process.
Provides the property of dispersing, and also prevents undesirable formation after reaction.
In order to provide diffusibility for substances to flow out of the system, for example,
carboxyl group, sulfo group, hydroxyl group, sulfo group
Alkali-soluble groups such as amoyl groups and e.g.
React by appropriately introducing a group that reduces the spreadability, such as a ru group.
All you have to do is balance the diffusivity between the front and rear. When the compounds of the present invention are classified based on their properties, for example, the following
The following classifications can be mentioned. CLΔSSI: Chromogenic dye-forming type Compounds belonging to this category have a compound in which the A part of general formula [1) is a carbon
The L i n k part of the puller residue binds to the active site of the coupler.
match. However, if Link is -NllSO2- (nitrogen source)
If the child is bound to the Coup part), it is located adjacent to the active site.
You can. The alkali is preferably dispersed in a small amount in the photographic material.
a soluble group and, for example, an alkyl group having 16 or less carbon atoms.
have Part A is coupled with the oxidized form of the color developing agent.
If a colored compound is produced during processing, the compound is
An alkali-soluble group is present in the A part so that it flows out of the system.
Contains an alkali-soluble group as a color developing agent
It is preferable to use In addition, if the B part forms a dye, the B part after the reaction
Part B has an alkali-soluble group so that the components flow out of the system.
It's nice to be there. For compounds belonging to this category, part A develops a negative color in the exposed part.
A dye image is created, but if the 17.8 part that flows out of the system is dye.
In this case, part 13 also flows out of the system after leaving part A.
Therefore, the compound represented by the general formula [1] remaining in the non-exposed area or
creates a positive image by the compound after color change. Part-1-
This compound has a small diffusivity, so it is not dispersed in the layer during the development process.
to create an unsharp blurred image. Furthermore, the following two are preferable among this class:
Examples include types. (Type A): Colored coupler type general formula [1
1] C0II+1- to Link2-r Co in the general formula [rl] is a coupler residue and is an alkali I
'If has a soluble group and is preferably
The resulting dye flows out of the photographic material system. The latter is an aryl group which may have a substituent, for example benzene.
or naphthalene type and a heterocyclic ring which may have a substituent
Groups such as inoxazole are preferred, and -.
The compound of the general formula [■] moves slightly in the
It preferably has a semi-diffusion prevention group, especially an Ar moiety.
1. stomach. 1. IIIk2 is -N=N-
or −C1]=. Some of these compounds have already been
As a lard coupler, for example, U.S. Pat.
No. 969, No. 2,688,538, No. 2゜706.6
No. 84, No. 2,808,329, No. 3,005,71
2, Belgian Patent @570,27], Special Publication No. 1977-
It is known as No. 32461. However, the present invention and these prior art do not completely limit the usage of the compound.
The purpose of using 1L is also different, and the effects obtained are different.
is completely alien. That is, the prior art
By the Co part, that is, the coupler part shown by the general formula [■]
The hue that occurs is the main absorption that forms images, so this
The principle is that the pigment generated from the part does not move.''2.1
The hue of the compound represented by the general formula [I] is based on the above main absorption wavelength.
This is the secondary absorption part that is different from the area. The present invention provides Cou 1
It is essential that the dye generated from one part be removed from the system.
and a compound represented by the general formula [n] or a compound after discoloration.
The hue of the compound is the same as the main absorption of the image forming layer. i.e. a silver halide layer combined with a compound of the invention.
For example, conventional light is a photographic material with a photosensitive wavelength range of
If so, it is a complementary color to the compound hue. Specifically, for example
For example, in the case of a green photosensitive negative layer, the colored layer of the prior art
Whereas the coupler uses a yellow compound in this layer, the present invention
In this case, a compound that is magenta or that changes color to magenta is used.
I am using it. (Type B): Active point substitution type general formula (Im) Coup-Link3Dye Cou I) is the same as general formula (II). Also, 1
．． i n k 3 is 1. of general formula [1]. i n k
is synonymous with , similar things are exemplified, and preferably
A group that produces alkali solubility after a pulling reaction, such as -〇
-1-SO2-N1 (-1-old ISO□- etc. is preferable)
stomach. Dye represents a dye moiety or a dye precursor moiety;
It is desirable to have alkali-soluble group, but % LInk3
Not required depending on the type. The compound represented by the general formula [■1] is present in a small amount in photographic materials.
In order to adjust the diffusion to
is preferable. The group includes chromogenic dyes and 1.1nki 1lye.
It is preferable to apply No. 4 to those with good dispersibility. still
, compounds belonging to this class are described in U.S. Patent No. 3.22
No. 7゜550, No. 3,476.563, etc.
However, like Type A, these prior technologies cannot be used at all.
The usage is different and the concepts of the present invention are not included. Immediately
Part of it uses the same colored coupler color correction as Type A.
When it is used and when it is diffused and transferred and it flows out.
This is clearly different from the aspect of the present invention when using a part for an image.
ing. Next, we found a group of compounds that did not produce a color image after the color reaction.
explain. CLASS II: Colorless coupling body forming type
For compounds belonging to this category, the A part of general formula [1] is C1, ^
Reacts in the same way as SSI compounds, but the reaction product is colorless
Therefore, it may remain in the layer after the coupling reaction.
. (TypeC): Weiss coupler type general formula [IV] Wcoup Link4 Dye Wcoup is, for example, R2COCl12 (R
2 is an alkyl, aryl, or heterocyclic group with 16 or less carbon atoms
alkyl), (Z completes 5 to 8 alicyclic rings, fused rings, or heterocycles)
In the atomic group, 83 represents an aryl residue. ). 1, ink 4 is -0-1-8- or -802-
shows. Dye is a dye residue preferably having an alkali-soluble group
or its precursor part, 1.1nk4-Dye is outside the layer
leaks to. In addition, this compound may contain alkali which may be present in the Dye moiety.
The compound itself diffuses slightly through the layer in cooperation with the soluble groups.
It is preferable to have a semi-diffusion preventing group so as to
It is preferable that it be in the W-coup part. CLΔ5S11! : Redox reaction type This classification
Compounds to which it belongs are CL^SSI or couplings like 11
No reaction is performed. Instead, it reacts with the oxidized developing agent.
This produces quinone, quinoid, etc., but this product
Reacts with an alkali in the developer or undergoes an intramolecular ring-closing reaction.
and release the pigment. (Typer) ): DRR compound membrane formula [V] FIJN Links Dye FIJN indicates a redox core, 2-93- or 4-
Phenol, 4-α-7toll, 1-β-7toll
, 2-hydroquinone, 3-indole, 4-pyrazolo
-5 residue, and L i n ks is -Hl5O7
-(nitrogen atom bonded to FIIN part), -O-, -S
O□-9-8-, etc., and Dye is a dye residue or its
It is a precursor part and preferably has an alkali-soluble group.
Delicious. So that the compound of general formula [V] diffuses slightly in the layer.
The Dye part may have alkaline solubility to
When using a semi-diffusion prevention group that cooperates with the FUN part,
It is preferable to attach Diffusion-resistant dye-forming small 4d, dispersible compounds are as described above.
It is itself a dye or its precursor, and it is also a color developing agent.
Generates a diffusion-resistant dye through reaction with the oxidized form of the main drug
However, due to this reaction, a new dye moiety is formed.
It may be a type of dye that does not form a new pigmented part.
, the dye part or its precursor part before reaction is subjected to development processing.
After treatment, it remains as a pigment part of the diffusion-resistant pigment.
You can. As a diffusion-resistant dye-forming non-diffusible compound, its function is
The following types are listed from above. Type ■ Pre-existing color due to coupling with oxidized color developing agent.
The dye part or its precursor is generated during the development process.
Generates a new pigmented area that is substantially the same color as the colored pigmented area
and Jti, a compound that makes diffusion resistant (pigment-forming type). This type is further divided into the following types.
Can be similar. Type 1-1 Pre-prepared by coupling with oxidized color developing agent
The pigment part or its precursor part disappears, and a new corresponding pigment part disappears.
The dye part or its precursor part has after the development process
Forms a pigmented part that is substantially the same color as the pigmented part
A compound that makes it resistant to diffusion. type! -2 Due to coupling with the oxidized form of the color developing agent,
The pigment part or its precursor part will not fade.
Furthermore, the dye part or the precursor part is further developed.
A pigmented part that is substantially the same color as the pigmented part that should be produced after the process.
A compound that forms and resists diffusion. Therefore this type
As a result of coupling with the oxidized form of the developing agent, the compound of
A pigment part derived from a preexisting pigment part or its precursor
In addition, it has diffusion resistance that also has a newly formed pigment part.
This will produce pigment (add-on type). Type I+ J: pre-existing for coupling with oxidized color developing agent
The pigmented part or its precursor part will not fade.
Diffusion resistant without forming new pigment parts
Compounds that do. Due to cross-oxidation with the oxidized form of color developing agent for type.
A compound that makes it resistant to diffusion. Each of the following two types will be explained in more detail. Type 11 compounds include, for example, the general formula (1-
Examples include compounds represented by 1). General formula CI-1) ^11. i n k +-B. In the formula, Δ1 is coupled with the oxidized developing agent and Link
- D, part is released according to the amount of the oxidized developing agent.
It is also an organic residue that can form a coupling dye.
R, L i n k is a group that connects the island and 01, B1
represents an organic residue. Specific examples of ^1 include phenols, Na71
・-ols, 5-pyrazolones, pyrazolotriazoles
, pyrazolotetrazoles, virazolobenraimigzo
compounds, indacilones, acylacetanilides, etc.
Can be mentioned. 1, i n k , for example -N=N-, -
(−)−. Examples include -S-, -SO□, -N8,000, and the like. here
, /I-N( is a nitrogen-containing heterocyclic residue, for example, succinimide
yl, imidoyl heptalate, pyridoyl, imidazolyl
, imigzolonil, benraimigzolil, higuntoy
ru, thiohyguntoyl, triazolyl, penztriazo
Lyle, urazolyl, 2゜4-dioxyoxacylyl, 2
,4~nooxonaazolyl, thianazolyl, tetra
Examples include Zolyl. As B1, 1. i n k + is like -N=N-
In the case of a chromophore, for example, an aryl group or a heterocyclic group, etc.
is preferred, and if Linkl is not a chromophore, the dye
(e.g. azo, anthraquinone, azomethine, indo
(phenol, indoaniline, etc.) residue or its precursor
Preferably, it is a body. A compound represented by the general formula (1-1) with the above structure
The object is r+, or A, -1, ink, -B, as a whole.
It can be a dye or its precursor. The compound represented by the general formula (1-1) is added during the development process.
8. Gives the property of slightly diffusing; is the dye or before
In the case of precursors, the dyes generated due to these are removed from the system.
The dye produced by the coupling process is resistant to spreading.
For example, carboxyl group, sulfo group, hydro
Alkali-soluble groups such as xyl group, sulfamoyl group and
and groups that reduce diffusivity, such as alkyl groups.
Just introduce it as appropriate to balance the diffusivity before and after the reaction.
. Type I-2 compounds include, for example, the following general formula C
Examples include compounds represented by I-2). General formula (1-2) % formula % In the formula, Dl represents a dye moiety or its precursor moiety, ^2
is coupled with the oxidized form of the developing agent to form a dye.
Dl represents a hydrous organic residue, but Dl is
There will be no departure from 2. =64- As a concrete example of ^2, the above-mentioned concrete example of ^ was shown.
Things can be mentioned. Examples of 01 include the dye residues listed as examples of 81 above.
and its precursors. Also ^2 is the coupling rank
It has a group capable of leaving rir upon coupling.
But that's fine. The releasable group may be a dye or a precursor thereof.
However, it is not essential that it be a dye or its precursor.
do not have. Also, the compound represented by the general formula (1-2) may be used during development.
It has the property of slightly diffusing, and the general formula [:I
-2] compound was coupled with the oxidized form of the developing agent.
To make the resulting dye diffusion resistant, e.g.
xyl group, sulfo group, hydroxyl group, sulfamoyl
alkali-soluble groups such as
The diffusion before and after the reaction can be improved by appropriately introducing groups that reduce diffusivity.
All you have to do is balance the dispersion. For example, when coupling to the coupling position of ^2
Separable alkali-soluble group or alkali-soluble group
It is also possible to bond a group containing . Type H compounds include, for example, the following general formula C11-
1]. General formula (■-1) -n2 In the formula, D2 has the same meaning as D1 in general formula r I-2).
and similar examples. Although W couples with the oxidized form of the developing agent, it
Compound residues that do not form pigments due to rings
represents. As W, for example, 5-pyrazolone nucleus, β-diketomethylene
Coupling at coupling position 16 of coupler residue such as ren group
After ringing, reactions to transfer to dye (e.g. oxidation reaction)
, elimination reaction) (e.g. methyl group, butyl group)
and bis-alkyl groups) and bis-alkyl groups.
Rubamoyl-aryloxymethane or bisalkyl
Carbamoyl-arylthiomethane compound residues are
Can be mentioned. In the general formula [:n-1], D2 is the coupling position of W
Some of the groups that do not cause the reaction that migrates to the dyes listed in
It is good to make it exist at a position other than the cambling position.
It may be combined at any position. Examples of compounds of type ■ include the following general formula [■-1]
Examples include those shown by. General formula ([[[-1) % formula % In the formula, D3 has the same meaning as ” in general formula [1-2]
and similar examples. Fun reacts with the oxidized product of the color developing agent to form the general formula [I
Has the function of making the compound shown in [1-1) diffusion resistant
Organic group with a hydroquinone nucleus, catefyl nucleus
Examples include groups having the following. Next, the diffusion-resistant positive compound will be explained in detail. For decolorization and discoloration, use small diffusible positive compounds.
are synonymous with those in . Due to the reaction between the oxidized color developing agent and the diffusion-resistant coupler.
Diffusion-resistant oxide compounds also act as a main developer in areas where dark-colored images occur.
It has the property of reacting with the oxidized form of the drug and producing a compound that becomes colorless or elutes from the system.
expressed. Also, color images due to diffusion-resistant couplers may occur.
In areas where the diffusion-resistant positive compound is
It remains colored. As a result, diffusion-resistant couplers
and the diffusion-resistant positive compound have an inverse relationship, i.e., the former
If it is a negative image, then it is necessary to form a positive image.
Become. Moreover, the diffusion-resistant positive compound is
This prevents the oxidized developing agent from diffusing from the layer containing the coloring agent.
The goal is to reach the layer containing the diffusion-resistant positive compound.
, an unsharp image, i.e. an unsharp positive image.
It will be formed. As the diffusion-resistant positive compound, for example, the following general formula (A-
Examples include compounds represented by 1). General formula (A-1) Δ, -LinkB3 In the formula, reacts with the oxidized developing agent to form Link-83 parts.
Depends on the content of the oxidized developing agent, it becomes colorless or
It is an organic residue that enables elution; 1. ■1 is ^3 and mouth
, B3 represents an organic residue. In addition, the compound represented by the general formula [A-1] is
A colored or color-changing compound that is resistant to diffusion in photographic materials.
Yes, but not caused by Δ3 and 1.1nk-B3 after reaction.
In the case of a compound whose product exhibits a hue unsuitable for image formation.
In some cases, after the reaction, the product is present in the hue system of the photographic material.
Balance the hydrophilicity or lipophilicity so that it can be eluted out of the system.
It is accompanied by a substituent. For example, ^3 in the general formula (A-13) is a color developer.
Coupling reaction with oxidized image agent produces colored or colorless
The residue of the coupler or the oxidized product of the developing agent that produces the product.
Examples include components that undergo cross-oxidation reactions. Specific examples of the former include, for example, 7 alcohols, naphtho, etc.
ols, 5-pyrazolones, pyrazolotriazoles,
Virazoloben limigsols, ingusolones, reeds
Ruacetanilides, RCOCH. (Z is, for example, 5 to 8 saturated or unsaturated alicyclic rings or
A group of primitives that complete a heterocycle, where 1' is an aryl residue
shows. ) residues are mentioned. As a specific example of the latter, for example, after oxidation, 7
IJ cleavage 1:: , k Q 1. ink li and L
Phenols that release Te13-5O2Nilθ, naph
Residues of tolls, indanones, and indoles, oxidized
Alka l) Ijll fissure 1m, J: l) 1
．． 1nk-11)-L Te, B-Oe, B”-8e I
Hydroquinone residues, acids that release r3-5o2e
After being converted into an intramolecular ring-closing reaction, 1. i n k
- Phenols that release B-so□e as B (details)
or U.S. Pat. No. 3,443,939, ibid.: +, 44
No. 3,94O, described in L44L941 +i.
Ru. ) residues are mentioned. For example, -N=NL, -o-
. /l -8-1-3O2-1-Nll-3O2-1-5O2-
Nll-T-NJanuary. Examples include -el+-, -white 1-, and the like. ■ku/I Here, -N,, -1- are nitrogen-containing heterocyclic residues, e.g.
Imidoyl basuccinate, imidoyl heptalate, pyridoy
imidazolyl, imigsolonyl, benzimidazo
Lyle, hydantoyl, thiohydantoyl, triazolyl
, penztriazolyl, turazolyl, 2,4-dioxy
Thioxazolyl, 2゜4-nooxothiazolyl, cyano
Examples include azolyl and tetrazolyl. Also, R is that
Alkyl, aryl, etc., each of which may have a substituent
. 13, ], ink is -N=N-, -C11-
For example, in the case of a chromophore such as an aryl group or a heterocyclic group,
Therefore, even if the organic residue has an auxochrome, it is preferable that the dye is
It may be a residue. Also, if Link is not a chromophore
dyes (e.g. azo, anthraquinone, azomethine)
, indo7er, indoaniline, etc.) or its
Preferably, it is a precursor of. Such configuration makes it possible to
The compound represented by formula (A-1) has 83 moieties or ^3
Link-8. Compounds that are colored or change color as a whole
sell. Diffusion during development into the compound represented by the general formula [A-1,]
L, [1, undesirable property after reaction]
To give the product diffusivity for elution out of the system
For example, carboxyl group, sulfo group, hydroxyl group
, alkali-soluble groups such as sulfamoyl groups, and e.g.
Introducing groups that reduce diffusivity, such as alkyl groups, as appropriate.
It is sufficient to balance the diffusivity before and after the reaction. When the compounds of the present invention are classified based on their properties, for example]
The following classifications are mentioned. C], ΔSSI: Coloring pigment-forming type Compounds belonging to this category are ^1 of the general formula (A'-1)
part is the coupler residue, and the link part is the coupler residue.
Connect to sex point. However, the ^1 part is a phenol residue or
7 toll residues, where 1, i n k is -NlIS
In the case of O2- (nitrogen atom is bonded to the Coup part), it is active.
The points may be adjacent to each other. And, in photographic materials, it is resistant to expansion.
A ballast group, such as a carbon number of 17 or more, is used to
It has an alkyl group of Δ3 part is oxidation of color developing agent
Coloring pigments produced by coupling with the body form images-1-
If inappropriate, the coloring dye may be washed out of the system during processing.
Should an alkali-soluble group be present in the third part such that
Use an alkali-soluble group as a color developing agent.
It is preferable that the 88 portion forms a dye or a precursor thereof.
If the reaction occurs, the 83 parts will flow out of the system.
preferably has an alkali-soluble group. Compounds belonging to this classification have a negative 3 part in the exposed area.
A colored dye image is created, but it is washed out of the system, and the 03 part is the dye.
In the case where the 83 part also flows out of the thread after separation from the ^3 part.
The general formula [shown in A-13] remains in the unexposed area.
Create a positive image using a compound that
Ru. Moreover, the edges of the positive image created by this compound are diffused.
During the development process, the above-mentioned
Forms an unsharp positive image in the layer. Furthermore, this kind of
Among these, the following two types are preferable:
can be mentioned. (TypeA): Colored coupler type general formula rA
-2] Coup -Link2-8r Co II 1)- in general formula 1:A-2) is a coupler residue.
It is preferable to have an alkali-soluble group in the color developing reaction.
The dye produced by the reaction is eluted out of the photographic material system. Ar is an aryl group which may have a substituent, for example benzene
Naphthalene type or naphthalene type and hetero which may have a substituent
Cyclic groups such as inoxazole are preferred;
The compound of general formula [A-23 is
It is preferable to have a diffusion-preventing group, especially in the Ar moiety. 1. i n k 2 is a chromophore, preferably -N=N-
Or -C11=. Some of these compounds have already been
As a lard coupler, for example, U.S. Pat.
No. 966, No. 2,888,538, No. 2,706.6
No. 84, No. 2,808,329, No. 3,005,71
It is known as No. 2, Special Publication No. 44-32461, etc. However, the present invention and these prior art do not completely limit the usage of the compound.
1 The purpose of use is also different, and the effects obtained are different.
is completely alien. That is, the prior art
C represented by general formula [A-2]. The hue produced by the up part, that is, the coupler part, is the image form.
Since this is the main absorption that causes the formation of
In principle, it is expressed by the general formula [8-2].
The hue of the compound is due to secondary absorption that differs from the article absorption wavelength range.
It is a part. In the present invention, the dye generated from the Coup portion is
It is essential to take it out of the system, and the general formula [A-2]
Is it expressed in ? The hue of F4# is determined by the main absorption of the image forming layer.
are the same. That is, in combination with the compound of general formula [A-2]
The photosensitive wavelength range of the washed silver halide layer is, for example,
If it is a national negative photographic material, the complementary color of the compound hue
It is. Specifically, for example, the green photosensitive layer will be explained.
and prior art colored couplers have a yellow compound in this layer.
In the present invention, a magenta-colored compound is used.
are doing. (TypeB): Active point substitution type general formula [A-3] Coup - Link' -Dye Cou 1+ is the same as general formula [A-2]. or,
1,111 and 3 are 1. of general formula [A-1]. i n k
is synonymous with , similar things are exemplified, and preferably
A group that produces alkali solubility after a pulling reaction, such as -〇
-1-So2-Nl+-, -NIISO□-, etc. are desirable.
Yes. Dye represents the dye part or its curved body part,
It is desirable to have an alkali Iff-soluble group, but I,
It is not essential depending on the type of ink3. Furthermore, this
Compounds belonging to the species class of U.S. Pat. No. 3,227.
No. 550, No. 3,476゜563, etc.
However, like Type A, these prior arts also have no usage method.
are different and do not include the concept of the present invention. That is, one
The part is the same as Type A and is used for color correction like a colored coupler.
The image shows the dye part that is leaking out due to diffusion transfer and the dye part that flows out due to diffusion transfer.
The present invention is clearly applicable when used for ! ! Unlike Mr.i
ing. Next, we will discuss a group of compounds that do not produce a color image after a color reaction.
I will clarify. c+, 8ssn: Colorless coupling body forming type
For compounds belonging to this class, the third part of the general formula [A-1] is C1
It reacts in the same way as the 8SSr compound, but there is no reaction product.
Since it is a color, it may remain in the layer after the cambling reaction.
stomach. (1'ypeC): Weis coupler type general formula (A-
4) Wcoup -1, ink"-Dye IA co 1111, for example, l112CO
CI+2- (R2 is alkyl, aryl, heterocycle
) (Z completes a 5- to 8-shell alicyclic ring, fused ring, or heterocyclic ring)
In the atomic group, R3 represents an aryl residue. ). stop
The -coup part is a compound represented by the general formula [A-4]
In order to make it diffusion-resistant, it is preferable to add a diffusion-preventing group such as carbon.
It has 17 or more groups. L i n k ' is 10-, -S- or 15o2-
show. Dye is a dye preferably having an alkali-soluble group or
, after reaction with its precursor residue, Link' Dye is outside the layer.
leaks to. C1, ASSIII: Redox reaction type This classification
Compounds belonging to the cup such as C1, ΔSSI straddled II
No ring reaction is performed. Instead, the oxidized developing agent
In response, quinine, quinoid, etc. are produced, but this production
The substance reacts with the alkali in the developer or undergoes an intramolecular ring-closing reaction.
The dye is released for the first time. (Typer') : DRR compound type general formula 1:
A-53 FUN-1,1nk5-Dye FIJ old soil redox 1u nucleus, preferably 2-1
3- or 4-phenol, 4-α-7tol, 1-β
-su7toll, 2-hydroquinone, 3-indole,
4-pyrazolone-5 residue, 1. i n k 5
-N11SO2- (nitrogen atom bonded to FUN part),
-0-, -5O2-, -S-, etc., and Dye is a pigment.
or its precursor residue and has an alkali-soluble group
It is preferable. In addition, a compound of general formula CA-5] is present in the layer.
The FUN section should preferably be provided with diffusion prevention measures to prevent movement of the FUN unit. 24 COOC, 21+□5 J-25 ++-26 l-27 J-28 l-29 11+1 Ul+ O2 l-32 l12 [J-33 [J-34 U-35 e HonSO□N(C41111)2 1. 1-39 p 0il OC21
1sU-46 tJ-478,. 1-50 tJ-55 - The positive compounds described above were synthesized according to general synthetic methods.
However, there are two main routes. i.e. one
synthesizes the pigment part in advance and finally converts the pigment part into oxychloride.
A suitable acid chloridating agent such as phosphorus or thionyl chloride
sul7ochloride or acid chloride and amine7 group by
It is a method of combining with another part that has
The synthesis method uses diazo coupling to add the dye in the final step.
This is how you get the pieces. In addition, in the case of a dye precursor, for example, after dye formation, the auxochrome is
It can be obtained by acylation or the like. The positive compound is a halogen containing the above-mentioned diffusion-resistant coupler.
in the silver halide emulsion layer and/or separately from the silver halide emulsion layer.
It is contained in the photographic constituent layer of. -1- The photographic constituent layers of the distribution are the silver halide emulsion layer
Although it does not have to be an adjacent layer, it is preferable that it be an adjacent layer.
Moreover, the positive compound itself is the main photosensitive area of the emulsion layer.
If the main absorption is in the silver halide emulsion layer,
position on the opposite side from the likely incident side during exposure.
This is preferable in order to prevent a decrease in sensitivity. Furthermore, upper distribution
The photographic constituent layers are a glossy light-sensitive silver halide emulsion layer and a color-sensitive layer.
It may be a photosensitive silver halide emulsion layer with the same properties.
Alternatively, it may be a non-photosensitive layer. In addition, the diffusion-resistant positive compound may be contained in a non-photosensitive state.
is preferable. When a carbon compound is included in the non-photosensitive layer, 1,
Developing agent generated by developing the memorizable silver halide emulsion layer
Of the oxidized forms of the drug, those that have diffused into the non-photosensitive layer
Bot compounds react to form Ansha-Pbodji images
I will do it. When using a positive compound, use it in conjunction with the compound.
0°01 to 1.0 per mole of diffusion-resistant coupler
0 mol is preferable, particularly 0.05 to 0.60 mol is preferable.
Yes. In addition, the method of adding it is the above-mentioned fogging release method.
Similar methods can be used for compounds. The silver halide emulsion of the present invention contains odor as silver halide.
Silver oxide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and
Any compound used in conventional silver halide emulsions such as silver and silver chloride
silver bromide, silver iodobromide
, silver chloroiodobromide is preferred. The silver halide grains used in silver halide emulsions are
13- by the neutral method, neutral method and ammonia method
It can be anything. The grains may be grown at times,
The seed particles may be grown after they are created. create seed particles
The method and growing method may be the same or different.
good. Silver halide emulsions contain halide ions and silver ions at the same time.
Even if they are mixed at times, in a liquid where either one is present, the other
may be mixed. In addition, critical growth of silver halide crystals
Mixing halide ions and silver ions while taking speed into account.
II in the gokama! Sequentially while controlling 118d
They may be generated by adding them simultaneously. this method
This results in a halo with a regular crystal shape and nearly uniform particle size.
Silver germide grains are obtained. In any step of the formation of 8g
Change the halogen composition of particles using the Convernoyon method
You may let them. Ammonia, thioether during growth of silver halide grains
The presence of known silver halide solvents such as , thiourea, etc.
I can do it. Silver halide grains are formed during the process of grain formation and/or
During the lengthening process, cadmium salts, zinc salts, lead salts, and thallium
Mu salts, iridium salts (including complex salts), rhodium salts (complex salts)
iron salts (including complex salts) and iron salts (including complex salts).
Metal ions are added using one type of
Alternatively, these metal elements can be contained on the particle surface.
Also, by placing it in an appropriate reducing atmosphere, the inside of the particles can be reduced.
Reduction sensitizing nuclei can be added to the part and/or the particle surface. The silver halide emulsion is produced after the growth of silver halide grains.
Unnecessary soluble salts may be removed or contained.
You can leave it on. When removing such salts, use a
Search Disclosure
(hereinafter abbreviated as RD) No. 17643
This can be carried out based on the method described in section (2). Silver halide grains have uniform densities within the grains.
Even with silver oxide composition distribution, the internal and surface layers of the grain
core/shell grains with different silver halide compositions.
Good too. A latent image is mainly formed on the surface of silver halide grains.
Particles such as
It may be a particle that is formed. Silver halide grains are cubic, octahedral, and dodecahedral.
It may have a regular crystal shape, or it may have a spherical or plate shape.
It may have an irregular crystal shape such as these
Particle odor 'C111O (+1 and l) I 1.1
The surface ratio fr: can be used as desired. Also, these results
Particles with various crystal shapes may also be particles with a composite of crystal shapes.
may be mixed. The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used. Silver halide emulsions have a large grain size distribution.
You may also use Wide emulsion with a grain size of 4ji
(referred to as polydisperse emulsion) may be used17, grain size
An emulsion with a narrow distribution of particles (referred to as a monodisperse emulsion).
A dispersed emulsion is defined by dividing the standard deviation of the grain size distribution by the average grain size.
When the value is 0.20 or less. here
In the case of spherical silver halide, the particle size is defined as the diameter.
In the case of particles with other shapes, the projected image is transformed into a circular image with the same area.
Shows the converted diameter. ) singly or in combination
It's okay. Also, polydisperse emulsion and monodisperse emulsion can be mixed and used.
It's okay. A silver halide emulsion consists of two or more types of halogens formed separately.
A silver emulsion may be used in combination. Silver halide emulsions can be chemically sensitized by conventional methods.
Wear. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
Noble 4 sensitization methods using gold and other metal compounds
Can be used alone or in combination. Silver halide emulsions are used as sensitizing dyes in the photographic industry.
Optically enhances the desired wavelength range using known dyes.
I can feel it. Although the sensitizing dye may be used alone, two types 1.
You may also use the words ``l'' and ``l'' together. With sensitizing dye
dyes that do not themselves have a spectral sensitizing effect, or visible
A compound that does not substantially absorb light and is a compound that enhances sensitizing dyes.
A supersensitizer that enhances the sensitization effect may be included in the emulsion.
. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dye, complex merocyanine dye, Holopolar
- Cyanine dyes, hemicyanine dyes, steryl dyes and
and hemioxal-7-al dyes are used. Particularly useful dyes include cyanine dyes, merocyanine color cords,
and a complex merocyanine pigment. Silver halide emulsions are used during the production of light-sensitive materials, during storage,
Or to prevent fog during photo processing or to improve photo performance.
During chemical ripening, the end of chemical ripening for the purpose of keeping the temperature constant.
and/or after completion of chemical ripening, the silver halide emulsion is
Before application, antifoggants or stabilizers are used in the photographic industry.
This can be achieved by adding a compound known as a fixing agent. Bingu (or protective colloid) of silver halide emulsion
Although it is advantageous to use gelatin as
gelatin derivatives, graft polymers of gelatin and other polymers,
Other proteins, sugar derivatives, cellulose derivatives, single
Or hydrophilic substances such as synthetic hydrophilic polymer substances such as copolymers.
Sex colloids can also be used. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
layer, other hydrophilic colloid layers are made of baingu (or
Hardener that cross-links (protective colloid) molecules and increases film strength
It can be hardened by using one or more types of
Pleasant. Hardener does not need to be added to the processing solution
Although it is possible to add a sufficient amount of photosensitive material to the hardening film,
It is also possible to add a hardening agent to the processing solution. For example, aldehydes, formaldehyde, glyoxate,
geltaraldehyde, etc.), N-methylolation
Compounds (tumethylol urea, methylol dimethyl hydant)
), dioxane derivatives (2,3-dihydroxydi
Nooxane, etc.), activated vinyl compounds (1, 3, 5 rivers, etc.)
Acryloyl-hexahydro-5-)riazine, 1.3
-vinylsulfonyl-2-propyl, etc.), active halide
rogen compound (2,4-dichloro-6-hydroxy-5
-) riazine), mucohalogen acids (mucochloric acid)
, mucophenoxychloric acid, etc.), etc.
can be used in combination. Silver halide emulsion layer and/or other hydrophilic coating of photosensitive material
A plasticizer can be added to the Lloyd layer to improve flexibility.
. Preferred plasticizers are those listed in RD17643, Section 3, A.
It is a compound listed above. The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials are
Water-insoluble or sparingly soluble
Containing a dispersion of synthetic polymers (latex)
I can do it. For example, alkyl (meth)acrylate, alkoxyal
Kill (Meta) Acrylic 1/-to, Grishitsur (Meta) Acrylic
rylate, (meth)acrylamide, vinyl ester (
(e.g. vinyl acetate), acrylonitrile, olefins,
Styrene etc. singly or in combination, or activated with these.
Rilic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid,
Hydroxyalkyl (meth)acrylate, sulfoal
Groups of kill (meth)acrylate, styrene sulfonic acid, etc.
It is possible to use polymers with polymers as polymer components.
Wear. The emulsion layer of the light-sensitive material is coated with aroma during the color development process.
Group primary amine developers (e.g. ρ-phenylenenoamine
derivatives, aminophenol derivatives, etc.) and carbon
A dye-forming coupler that performs a coupling reaction to form 11 dyes.
- is used. The dye-forming coupler is present in each emulsion layer.
On the other hand, a dye is formed that absorbs the sensitivity spectrum of the emulsion layer.
It is usually selected as a blue-sensitive emulsion.
A yellow dye-forming coupler in the layer and a green-sensitive emulsion layer.
A magenta dye-forming coupler is present in the red-sensitive emulsion layer;
Dye-forming couplers are used. However, depending on the purpose
Silver halide is used in a different way than in combination.
Even if you make color photographic materials, it's not possible. These dye-forming couplers are called ballast groups in the
It has a group with 8 or more carbon atoms that makes the coupler non-diffusive.
It is desirable to do so. Also, these dye-forming couplers are 1
Four molecules of silver ions are reduced to form a molecular dye.
Even with the 4-isomerism that needs to be
Either diisomerism, which only requires that the ion is reduced, is acceptable. Pigment-forming couplers are colors that have the effect of color correction.
Coupling with the decoupler and the oxidized form of the developing agent
Development inhibitors, development accelerators, bleach accelerators, developers,
Silver halogenide solvent, toning agent, hardener, fogging agent, anti-capri
11-agents, chemical sensitizers, spectral sensitizers, and desensitizers.
Contains compounds that release 7 photographically useful fragments.
be done. Among these, development inhibitors are released during development.
, the coupler that improves image sharpness and image graininess is D.
It is called an IR coupler. Instead of the DIR coupler, the current
Coupling reaction with the oxidized form of the image agent produces a colorless compound.
using a DIR compound that simultaneously releases a development inhibitor.
You can stay there. The DIR Kabufu and old R compounds used include
One in which the inhibitor is directly bound to the pulling position, and the other in which the inhibitor is bonded directly to the pulling position.
It is attached to the coupling position via a valent group, and the coupling
The intramolecular nucleophilic reaction and the separation of makuuchi separated by the
The binding is performed so that the inhibitor is released by an intramolecular electron transfer reaction, etc.
combined (timing DIR coupler and timing
(referred to as DIR compounds). In addition, the inhibitor is also released.
Those that are diffusible after withdrawal and those that are not so diffusible
can be used alone or in combination depending on the purpose
. Oxidized product of aromatic primary amine developer and force/sampling reaction
colorless couplers (competitive couplers) that react well but do not form dyes.
(also called color) in combination with a dye-forming coupler.
It's also good. As yellow dye-forming couplers, known acylacetate
Toanilide couplers can be preferably used. Among these, benzoylacetanilide and pivalo
Compounds based on ylacetanilide are preferred. Available yellow
Specific examples of color-forming couplers include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3,265.506, No. 3,4
No. 08,194, No. 3,551,155, No. 3,
No. 582,322, No. 3,725,072, No. 3
．． No. 891°445, West German Patent No. 1,547,888,
West German Application No. 2.219.917, No. 2,261.3
No. 61, No. 2,414,006, British Patent No. 1,42
No. 5.020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 48-73147, 50-63
No. 41, No. 50-87650, No. 50-123342
No. 50-130442, No. 51-21827,
No. 51-102636, No. 52-82424, No. 5
Described in No. 2-115219, No. 58-95346, etc.
It is something that was given. As a magenta dye-forming coupler, known 5-pyrazo
Ron-based couplers, Virazolobenlimigzol-based couplers
-, pyrazolotriazole couplers, open-chain acylacetate
Uses tonitrile couplers, ingzolone couplers, etc.
I can be there. Specific examples of magenta coloring couplers that can be used include, for example,
National Patent No. 2, 600.788, National Patent No. 2.983,6
No. 08, No. 3,062,653, No. 3,127,
No. 269, No. 3,311゜476, No. 3.419
, No. 391, No. 3,519.429, No. 3,55
No. 8,319, No. 3,582.322, No. 3.6
No. 15,506, No. 3,834,908, No. 3,
No. 891,445, West German Patent No. 1,810,464, West
German patent application (OLS) No. 2,408,665, 2,
No. 417,945, No. 2,418.959, No. 2,4
No. 24,467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 1973
-74027, 49-74028, 49-12
No. 9538, No. 50-60233, No. 50-1593
No. 36, No. 51-20826, No. 51-26541
, No. 52-42121, No. 52-58922, No. 5
3-55122, Japanese Patent Application No. 110943, etc.
Examples include those listed below. Cyan dye-forming couplers include phenol or carbonate.
7 toll couplers are commonly used. Available systems
Specific examples of uncolored couplers include U.S. Patent No. 2,42
No. 3,730, No. 2,474.293, No. 12.8
No. 01,171, No. 2.895,826, No. 3,
No. 476.563, No. 3.737,326, No. 3
, No. 758, 308, revised specification No. 3゜893.044
, JP-A-47-37425, JP-A No. 50-10135,
No. 50-25228, No. 50-112038, No. 5
No. 0-117422, No. 50-130441, etc.
What is described in JP-A No. 58-987'31
Couplers described in this publication are preferred. Pigment formation that does not require adsorption to the silver halide crystal surface
coupler, colored coupler, DIR coupler, DIR
Compounds, image stabilizers, color fog prevention agents, ultraviolet absorbers
, optical brighteners, etc., hydrophobic compounds are
Various methods such as TEX dispersion method, oil-in-water emulsion dispersion method, etc.
can be used for hydrophobic compounds such as couplers.
It can be selected as appropriate depending on the chemical structure and the like. underwater
Oil drop emulsion dispersion method disperses hydrophobic additives such as couplers.
Conventionally known methods can be applied to reduce the boiling point to 150
If necessary, add low boiling point organic solvents to high boiling point organic solvents of
Gelatin is dissolved in water using a combination of
Stirring using a surfactant in a hydrophilic baguette such as a liquid
homogenizer, colloid mill, 70-jitomi
Emulsify and disperse using a dispersion device such as a mixer or an ultrasonic device.
After that, it can be added to the desired hydrophilic colloid liquid.
. A process that removes low-boiling organic solvents from dispersions or at the same time as dispersion.
You can take your time. High boiling χ solvent does not react with the oxidized form of the developing agent7
E/-luminium conductor, 7-tar acid alkyl ester, phosphoric acid
Esters, citrate esters, benzoate esters, alkaline
Kylamide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a boiling point of 150° C. or higher is used. Low boiling or water soluble with or in place of high boiling solvents
Organic solvents can be used. Low boiling point, virtually insoluble in water
Ethyl acetate and propyl acetate are used as organic solvents.
, butyl acetate-F1 butanol, chloroform, tetrasalt
carbon dioxide, nitromethane, nitroethane, benzene, etc.
Le. Dye-forming couplers, DIR couplers, colored couplers
, DIR compound, image stabilizer, color antifoggant, ultraviolet light
Absorbers, optical brighteners, etc., such as carboxylic acids and sulfonic acids,
When it has an acid group, it can be used as an alkaline aqueous solution.
It can also be incorporated into aqueous colloids. Using a hydrophobic compound alone or in combination with a low-boiling point solvent
Dissolved in a solvent and dispersed in water using mechanical or ultrasonic waves.
Anionic surfactants,
Ionic surfactants, cationic surfactants and amphoteric surfactants
Surfactants can be used. Between emulsions N of light-sensitive materials (between the same and color-sensitive layers and/or between different color-sensitive layers)
between the color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent
The movement may cause color turbidity, deterioration of sharpness, or graininess.
11- To prevent color from becoming noticeable, use a color fog prevention agent.
Can be used. The color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer is provided between adjacent emulsion layers, and the intermediate layer contains
Good too. Photosensitive materials contain image stabilizers to prevent deterioration of dye images.
Can be used. Compounds that can be preferably used
The product is as described in Item J of RD17643. Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials are photosensitive.
Turning caused by electrical discharge caused by material becoming charged due to friction, etc.
11- To prevent damage and image deterioration due to ultraviolet rays.
may contain an ultraviolet absorber. Magenta color due to formalin during storage of material
In order to prevent deterioration of elementary couplers, etc., photosensitive materials
A formalin scavenger can be used. Dyes, ultraviolet absorbers, etc. are added to the hydrophilic colloid layer of photosensitive materials.
When containing them, they can be used as a medium such as cationic polymer
It may be mordanted with a dye. Silver halide emulsion layer and/or other hydrophilic material of photosensitive material
Addition of development accelerators, development retardants, etc. to the sexual colloid layer to change the developability.
Chemical compounds and bleach accelerators can be added. development accelerator
The compound that is preferably used as RD176 is
It is a compound described in No. 43, Section XXT, Section B-r), and has a development slowness.
The spreading agent is a compound described in Section XXI, Section E of No. 17643.
Ru. Black and white developing agents and/or
may use its precursor. The emulsion layer of photographic light-sensitive materials has increased sensitivity and contrast of -1
- Polyalkylene oxide or
is its ether, ester, amine derivative, thioester, etc.
ether compounds, thiomol 7-olins, quaternary ammonium
compounds, urethane derivatives, urea derivatives, imiguzol derivatives
1 even if it includes conductors etc. Photosensitive materials are used to emphasize the whiteness of white backgrounds and to
Optical brighteners can be used to make the coloration less noticeable.
Wear. Formulas that can be preferably used as optical brighteners
The compound is described in section v of R1117643. The photosensitive material includes a filter layer, an antihalation layer, and an ink layer.
An auxiliary layer such as a radiation prevention layer can be provided.
. In these layers and/or in the emulsion layer, sensitization may occur during development.
Contains dyes that are leached or bleached from the optical material.
You may be forced to do so. Such dyes include oxonol dyes.
dye, hemioxol dye, styryl dye, merocyanine
Examples include cyanine dyes, cyanine dyes, azo dyes, etc.
Ru. Silver halide emulsion layer and/or other hydrophilic material of photosensitive material
Addition of sex colloid 1 reduces the bias of photosensitive materials and improves the ease of addition.
, a matting agent for the purpose of preventing photosensitive materials from sticking to each other.
can be added. Any matting agent can be used.
For example, silicon dioxide, titanium dioxide,
Magnesium, aluminum dioxide, barium sulfate, charcoal
Calcium acid, polymers of acrylic acid and methacrylic acid
and their esters, polyvinyl resin, polycarbonate
and styrene polymers and their copolymers.
can give. The particle size of the matting agent is 0.05μ to 10μ.
is preferable. The amount added is preferably 1 to 300 g/m2.
Delicious. A lubricant can be added to photosensitive materials to reduce sliding friction.
Wear. Antistatic agents can be added to photosensitive materials to prevent static electricity.
Wear. The antistatic agent is added to the band on the side of the support where the emulsion is not laminated.
May be used in anti-static layer, emulsion layer and/or support.
Protective rollers other than the emulsion layer on the side where the emulsion layer is laminated
may be used for id/g. Preferably used charging
The inhibitor is a compound described in RD17643 No.
It is. Photographic emulsion layer and/or other hydrophilic colloid layer of light-sensitive material
Improved applicability, antistatic properties, improved slipperiness, emulsification and dispersion,
Adhesive adhesive 1, improved photographic properties (development acceleration, hardening, sensitization, etc.)
Various surfactants can be used for purposes such as
Ru. The support used in the photosensitive material of the present invention includes a-olefin.
fin polymers (e.g. polyethylene, polypropylene)
, ethylene/butene copolymer), etc.
Flexible reflective supports such as synthetic paper, cellulose acetate, cellulose nitric acid
Lulose, polystyrene, polyvinyl chloride, polyethylene
Nterephthalate, polycarbonate, polyamide, etc.
Films made of semi-synthetic or synthetic polymers and films of these
Flexible support with reflective layer on film, glass, metal,
Including pottery etc. Photosensitive materials are treated with corona discharge and ultraviolet light on the support surface as necessary.
Directly or on the support surface after radiation irradiation, flame treatment, etc.
adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness,
Anti-halation I1. properties, friction properties, and/or other
Through the undercoat layer of 1-layer wire-11, which has the characteristics of
Even if it is applied, it is still small. Thickening to improve coating properties when coating photosensitive materials
Agents may also be used. Also, for example, hardeners, which have a high reactivity.
To speed up the process, adding it to the coating solution in advance will reduce the delta before coating.
Static mixer
It is preferable to mix immediately before application. As for the coating method, apply two layers of 2 inserts-L at the same time.
Extrusion thin coating and curtains
Coatings are particularly useful, but depending on the purpose, packaging
A wet coating is also used. Also, the coating speed can be selected arbitrarily.
I can do it. Examples of surfactants include, but are not limited to, saponi.
natural surfactants, alkylene oxides, glycerin, etc.
7-ion surfactants such as phosphorus and glycidol, high
class alkyl amines, quaternary ammonium salts, pyridine
and other heterocycles, phosphonim and sulfonyl
Cationic surfactants such as aluminum, carboxylic acids, sulfones
Acidic groups such as acid, phosphoric acid, sulfuric acid ester, phosphoric acid ester, etc.
anionic surfactants, amino acids, amino sulfonate containing
acids, sulfuric acid or phosphoric acid esters of amino alcohols
Ampholytic surfactants such as the following may be added. Also, for the same purpose, fluorosurfactants are used.
It is also possible to To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing is a color development process.
process, bleaching process, fixing process, washing process and necessary
A stabilization treatment process is performed as necessary, but treatment using a bleach solution is not recommended.
One-bath bleaching instead of physical and fixer processing steps
A bleach-fixing process can also be performed using a fixer.
Color development, bleaching, and fixing can be performed in one bath.
A monobath processing process using a one-bath development bleach-fix processing solution.
You can also do this. In combination with these treatment steps, there is a predural treatment step, and
Neutralization process, stop 1 fixed treatment process, posterior dural treatment process, etc.
You may go. In these treatments, the color development process
Instead, use a color developing agent or its precursor as a material.
It is contained in the liquid and developed using an activator solution.
An activator treatment step may be performed, or the monobar
The process ends with applying an activator treatment to the base treatment. Among these processes, typical processes are shown below. (these
As the final process, the treatment includes a water washing process, a water washing process, and
and stabilization treatment steps. )・Color development processing
Process - bleaching process, fixed fixing process, color development process - bleach-fixing process, pre-shelf film process
Process - Color development process - Stop 1 Constant fixation process - Washing process
Process - Bleaching process Constant fixation process - Washing process -
Post-hardening process/Color development process - Water washing process - Supplementary color development process
Process - Stop treatment process - Bleach treatment process Constant fixation treatment process / Activator treatment process - Bleach-fix treatment process / Activator treatment process
Beta treatment process - Bleaching process Constant fixation treatment process / Monobath treatment process The treatment temperature is usually selected in the range of 10°C to 65°C.
, the temperature may exceed 65°C. Preferably 25
6 Color developers processed at temperatures between 6 °C and 45 °C are generally alkaline water containing a color developing agent.
Consists of a solution. The color developing agent is an aromatic primary amine color forming agent.
It is a developing agent, and contains amine phenol and p-phenylene.
Contains non-amine derivatives. These color developing agents
can be used as salts of organic acids and inorganic acids.
Salt isoic acid, sulfate, 1)-toluenesulfonate, sulfite
Using acid salts, shelerate salts, benzenesulfonate salts, etc.
I can do it. These compounds are generally about 0.0% in color developer 11.
Concentration of 1 to 30 g, more preferably 1 p of color developer.
It is used at a concentration of about 1 to 15 Fi. 0,11? Yo
If the amount added is too small, sufficient color density cannot be obtained. - For example, the aminophenol developer described in 0-
Amino 7er/7-el, 1]-amino 77er/-er, 5-amino
Nor-2-oxy-toluene, 2-amino-3-oxy-
Toluene, 2-oxy-3-ami/-1,4-tumethyl
-Includes benzene, etc. Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound
, alkyl groups and phenyl groups may be substituted or
or may not be replaced. Especially useful among them
An example of a compound is N-N-tumethyl-p-7x nylenedi
Amine [ljM, N-methyl-p-phenylenediamine
Hydrochloride, N,N-dimethyl-p-phenylenediamine salt
acid salt, 2-amino-5-(N-ethyl-N-dodecyla
Mi/)-)luene, N-ethyl-N-β-methanesulfo
Amidoethyl-3-methyl-4-ami/7 = '
) N-sulfur Wl salt, N-ethyl-N-β-hydroxyethyl
Ruaminoaniline, 4-amino-3-methyl-N,N-
Noethylaniline, 4-ami/-N-(2-methoxye
ethyl)-N-ethyl-3-methylaniline-p-)rue
Examples include sulfonate and the like. In addition, the above color developing agents may be used alone or in combination of two or more.
It may also be used as Furthermore, the -1- color developing agent is
It may be incorporated into a color photographic material. In this case, the silver halide color photographic light-sensitive material is color developed.
Treat with alkaline solution (activator solution) instead of liquid.
It is also possible to bleach immediately after treatment with alkaline solution.
It is fixed. The color developing solution used in the present invention is a commonly used developer.
Alkaline agents such as sodium hydroxide, potassium hydroxide
, ammonium hydroxide, sodium carbonate, potassium carbonate
, sodium sulfate, sodium metaborate or borax etc.
It may further contain various additives such as benzyl
Alcohols, alkali metal halides, e.g. carbon bromide
or potassium chloride, or as a development regulator.
For example, hydroxyl as a preservative, such as citradinic acid.
It may also contain minerals or sulfites. In addition, various erasers
Foaming agents and surfactants, as well as methanol and dimethylform.
Amide or dimethyl sulfoxide etc. 8! solvent etc.
It can be contained as appropriate. 1) 11 of the color developing solution used in the present invention is usually 7 or more.
and preferably about 9 to 13. In addition, the color developing solution used in the present invention may include
Noethylhydroxyamine, tetron as an antioxidant
acid, tetronimide, 2-anilinoethanol, dihydre
Roxyacetone, aromatic secondary alcohol, hydroxam
acid, pentose or hexose, pyrogallol-1,
3-methyl ether etc. may be contained. The color developing solution used in the present invention contains a metal ion sequestering agent.
Then, various chelating agents are used in combination. example
For example, the chelating agent may be ethylenediaminetetraacetic acid,
Amine polycarboxylic acids such as tylenetriaminopentaacetic acid, 1
-hydroxyethylidene-111'-diphosphonic acid, etc.
Organic phosphonic acid, aminotri (methylenephosphonic acid)
Or aminopolymer such as ethylenediaminetetraphosphate
Oxygenates such as phosphonic acid, citric acid or gluconic acid
Rubonic acid, 2-phosphonobutane 1.2.4-tricarbo
Phosphonocarboxylic acids such as phosphoric acid, tripolyphosphoric acid or
Polyphosphoric acid such as hexametaphosphoric acid, polyhydroxylation
Examples include compounds. As mentioned above, the bleaching process is performed at the same time as the fixing process.
may be performed or may be performed individually. Metal complex salts of organic acids are used as bleaching agents, such as bleaching agents.
Ricarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid
An organic acid such as acid that contains metal ions such as iron, cobalt, and copper.
The one listed is used. The most preferred of the above organic acids
Preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids.
Examples include carboxylic acids. Specific examples of these include
Diaminetetraacetic acid, diethylenetriaminepenta
Acetic acid, ethylenecyamine-N-(β-oxyethyl)
-N, N'. N'-triacetic acid, propylenenoaminethitraacetic acid, nitrate
Lilotriacetic acid, cyclohexanediaminetetraacetic acid,
minodiacetic acid, dihydroxyethylglycincitric acid (or
tartaric acid), ethyl ether diamine tetraacetic acid, glyco
ether diamine tetraacetic acid, ethylene diamine tetraacetic acid
Trapropionic acid, 7-enylenediaminetetraacetic acid, etc.
can be mentioned. These polycarboxylic acids contain alkali metal salts, ammonium
It may be a water-soluble amine salt or a water-soluble amine salt. these
Bleach is 5-450. /'/, more preferably 20-2
Use at 50g/I. In addition to the above-mentioned bleaching agents, the bleaching solution may contain preservatives if necessary.
A liquid having a composition containing sulfite as an agent is applied. or
, ethylenecyaminetetramerous acid (■1) complex salt bleach
containing large amounts of halides such as ammonium bromide.
It may also be a bleaching solution consisting of an added composition. Said halogen
In addition to ammonium bromide, hydrochloric acid,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide
ammonium iodide, sodium iodide, potassium iodide, ammonium iodide
You can also use ``mu'', etc. The bleaching solution used in the present invention includes Japanese Patent Application Laid-Open No. 46-280
, Special Publication No. 45-8506, No. 46-556, Belgium
-Patent No. 770,910, Special Publication No. 1988-8836,
No. 53-9854, JP-A-54-71634 and the same
Various bleach acceleration methods described in No. 49-42349 etc.
agents can be added. The ρ11 of the bleaching solution is 2.0 or more -I- is used, but -shell
4.0 to 9.5, preferably 4.5 to 8
．． 0, most preferably 5.0-7.0
. Fixers with commonly used compositions can be used.
can. As a fixing agent, it is used in normal fixing processing.
A compound that reacts with silver halide to form a water-soluble complex salt.
compounds, such as potassium thiosulfate, sodium thiosulfate
, thiosulfates such as ammonium thiosulfate, thiocyanine
Potassium thiocyanate, sodium thiocyanate, thiocyanate
Thiocyanates such as ammonium, thioureas, thioethers
A typical example is Teru et al. These fixatives are 5
It is used in an amount of 1g/1 or more, within the range that can be dissolved, but generally
is used at 70 to 250 g/&. Furthermore, the fixing agent is one of them.
can be included in the bleach tank, or vice versa.
A portion can also be contained in the fixing tank. In addition, the bleaching solution and/or fixing solution contains boric acid, borax, and sodium hydroxide.
Thorium, potassium hydroxide, sodium carbonate, potassium carbonate
um, sodium bicarbonate, potassium bicarbonate, acetic acid, acetic acid
Various pHlll concentration such as sodium, ammonium hydroxide, etc.
Contain the agent singly or in combination of two inserts.
can be done. Furthermore, various optical brighteners and antifoaming agents
Alternatively, a surfactant can also be included. or,
Hydroxylamine, hydrazine, aldehyde compounds
Preservatives such as bisulfite adducts, amino/polycarboxylic acids, etc.
Organic chelating agents or nitro alcohols, nitrates, etc.
stabilizers, hardeners such as water-soluble aluminum salts, methane
trimethyl sulfamide, trimethyl sulfoxide, etc.
This can be achieved by appropriately containing an organic solvent or the like. The IIH of the fixer is 3.0 or higher, but generally 1
This is used in the range of 4.5 to 10, preferably in the range of 5 to 9.5.
most preferably from 6 to 9. The above bleaching process as a bleaching agent used in the bleach-fix solution
Preferred examples include metal complex salts of organic acids described in
The bleaching process also includes new compounds and concentrations in the processing solution
It is the same as in the process. In addition to the above-mentioned bleaching agents, the bleach-fix solution contains silver halide stabilizers.
Contains adhesive and, if necessary, sulfite as a preservative.
A liquid with a composition having the following composition is applied. Also, ethylenediamine
Iron acetate (Ill) complex salt bleach and the above silver halide determination
Small amounts of other halides such as ammonium bromide in adhesives
A bleach-fix solution consisting of an additive composition or, conversely, a bromide solution
From a composition containing a large amount of halides such as ammonium
bleach-fix solution, and even ethylene diamine iron acetate (
I[t] Complex salt bleach and large amounts of ammonium bromide
A special bleaching formula with a combination of halides
It is also possible to use a liquid. As the halide,
, ammonium bromide, hydrochloric acid, hydrobromic acid, odor
Lithium chloride, sodium bromide, potassium bromide, sodium iodide
Lithium, potassium iodide, ammonium iodide, etc. are also used.
It ends with that. Silver halide fixer that can be included in bleach-fix solution
As a fixing agent - List the fixing agents described in the fixing process.
be able to. The concentration of the fixing agent and its inclusion in the bleaching fixing solution
See above for pH adjustment and other additives that can
The fixing process is the same as in the culm. 1) 11 of the bleach-fix solution is used at 4.0 or higher, but
Generally used in the range of 5.0 to 9.5, preferably 6.0 to 9.5.
8.5, most preferably between 6.5 and 8.5.
Ru. [Example] Examples of the present invention will be described below.
The embodiments are not limited to these. In all of the following examples, silver halide photographic light-sensitive materials
Unless otherwise specified, the amount added in the ingredients is per +n2.
shows. Also, silver halide and colloidal silver are converted into silver.
Indicated. The following is added to the triacetyl cellulose film support-1-
By sequentially forming each layer having the composition shown in the following from the support side,
Multilayer color photographic element sample-1 was prepared. Note that the dry film thickness was adjusted by the amount of gelatin. Sample-1 (comparison) 1st layer; Halley sidin prevention/l (IIC-1) Black coat
gelatin layer containing roid silver. Dry film thickness 2.0μl11 12 layers; middle layer (+, 1..)? , emulsified dispersion of 5-di-1-octylhydroquine
gelatin layer containing. 3rd layer; low sensitivity red-sensitive silver halide emulsion layer (R1, -1
) Average particle size (r) 0.30 μIII, Agl 6 mol
Monodisperse emulsion (emulsion 1) consisting of 8 BBr I containing % - m - silver coverage 1.8 I? /l1
12 Sensitizing dye 1 ------- 6X10-5 moles per mole of silver Sensitizing dye n ------- 1,0XIO-'S molesian coupler per mole of silver
- (C-1) ----0.06 per mole of silver
Mol colored cyan coupler (CC-1) ---- Silver
1 mole to 1 mole, ooa mole 1'llR compound (D-1) ----- to 1 mole of silver
and 0.0015 mol DIR compound (r) -2> ---- per 1 mol of silver
and 0.002 mol dry film thickness 2.7μ button tlsA layer; commercial sensitivity red-sensitive silver halide emulsion N (old (-
1) Average particle size (r) 0.5 μm + Agl 7.0 m
Monodisperse emulsion (emulsion ■) consisting of 8 gBrl containing 1.0 g/m'' silver coating weight
Sensitizing dye r ------- 3 x 10-' moles per ii mole Sensitizing dye n ----- t, ox 10-5 moles cyan coupler per mole of silver
- (C-1) ----0.02 per mole of silver
Mol colored cyan coupler (CC-1') -----
0.0015 mol per mol of silver nlR compound (r) -2) ----- per mol of silver
0.001 mol Dry film thickness 2.0μ Mark No. 5N: Intermediate layer (1,L,) Same as the second layer, gelatin layer. Dry film thickness 1. θμ Theory No. 6 JN: Low-sensitivity green-sensitive silver halide emulsion layer (G1
．． -1) Emulsion -1----For single coated silver 1.5) H/P
2 Sensitizing dye 1 ---- 2.5X 10-5 mol sensitizing dye n per 1 mol silver
------ 1.2X 10-5 mole magenta cap per mole of silver
color (Ml)---0.050 mol per mol of silver Colored magenta coupler (CM-1')---=-1 mol of silver
0.009 mol per mole of DIR compound (r) -1) -, ---- per mole of silver
0.0010 mol DIR compound (r) -3) ---- 0.0010 mol per mol of silver
0.0030 mol dry film thickness 2.7 μ theory 7th layer; high sensitivity green sensitive silver halide emulsion layer (Gl+-1
) Emulsion-n----Amount of silver coated per coat 1.4&/1l12 sensitization
Dye r------ 1 mole of silver 1 large 1.5x 10-s mole sensitizing color
element n ---- 1.0XIO-5 mole magenta coupler per mole of silver
- (M -11---0.020 per mole of silver
Molcolor Magenta Coupler (CM-1) ----- Silver
0.002 mol per mol DIR compound (D-3) ----- per mol silver
0.0010 mol Dry film thickness 2.0 μ [n 8th layer; Yellow filter N (yc-i) Yellow color
milk of idosilver and 2,5-di-t-octylhydroquinone
a gelatin layer containing a gelatinized dispersion; Dry film thickness 1.0 μm 9th layer; low sensitivity blue-sensitive silver halide emulsion layer (IIL-1
) average particle size 0.48 μm, containing 6 mol% of ^sr.
Monodispersed emulsion consisting of 0r+ (emulsion ■) -- 1 silver coating amount 0.9 g/2 more
Color Sensitive Cord V------ 1.3X 10-5 mole yellow cap per mole of silver
(Y -1) ----0.0 per mole of silver.
34 mol dry film thickness 3.2 μ Kawa No. 101f4; High sensitivity blue-sensitive emulsion M (formerly 1-1) average grain
Diameter 0.8μI11. 8g + 8gli containing 15 mol%
Dispersed emulsion (emulsion ■) consisting of r (11 silver coating i0,5H/m
2 Sensitizing dye V ---- 1.0 x 10-5 mol yellow coupler per mol of silver
- (Y -1) ----0.1 per mole of silver
3 mol 1) Ill compound (D-2) ----- to 1 mol of silver
(1,0015 mol Dry film thickness 2.0 μl $111: First protective layer (Prol) Silver iodobromide (Agl 1 mol% average grain size 0.07 μl) Silver
Coating amount: 0.5 g/l 112 Gelatin layer containing ultraviolet absorbers UV-1 and UV-2. Dry film thickness 1.5 μω 12th layer; 2nd protective layer (pro-2) polymethyl meta
Acrylate particles (diameter 1.5 μ'0) and formalin
The dry film thickness of the gelatin layer containing Kabennoya (IIS=1) is 1.0 μm.In addition to the composition described in 1.
1) and a surfactant were added. The total dry film thickness was 22.1μ+o. The compounds contained in each layer of Sample 1 are as follows. Sensitizing dye l; anhydro 5,5'-dichloro-9-ethyl
ru-3,3'-c(3-sulfopropyl)thiacarbo
Cyanine hydroxide sensitizing dye ■; Anhydro 9-ethyl-3,3'-di(
3-sulfoprovir)-4,5,4',5'-dibenzo
Thiacarbocyanine hydroxide sensitizing dye l; anhydro5t 5'-nophenyl-9=
Ethyl-3,3'-di(3-sulfopropyl)oxa
Carboxyanine hydroxide sensitizing dye ■; Anhydro 9-ethyl-3,3'-di(
3-sulfoprovir)-5,6,5',6'-dibene
Zoxacarbocyanine hydroxide sensitizing dye V;
lopyru)-4,5-benzo-5-nomethoxythiacyani
Ping 2 Ping \ Below thread C-1 CC-1 O) 1 M-1 rθ V-1 1l cnuJt) V-2 11°. -610 Next, as shown in Table 1, from sample 1, the fifth layer and the sixth layer
, a compound that releases a fogging agent into the seventh layer, and an anhydrous compound.
- Adding a compound that forms a positive image, and also increasing the dry film thickness.
Sample 2□-15 is the same as sample 1 except that the total sum of
It was created. Each sample No. 001 to No. 15 created in this way was exposed to white light.
Use wedge exposure and square wave chart [Contact exposure
After that, the following development treatment was performed. The change in dry film thickness is adjusted by the amount of gelatin, and the thickness of each layer is
The dry film thickness change rate was kept the same. Treatment process (38℃) Coloring phenomenon 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixing for 3 minutes and 15 seconds Washing with water for 6 minutes and 30 seconds Stabilizing for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the processing solution used in each processing step is as follows.
be. [Coloring phenomenon liquid] 4-Amino-3-methyl-N-ethyl-N-(β-hydro
(oxyethyl)-aniline sulfate
4.75g anhydrous sodium sulfite
4.25g hydroxylamine 1/2 sulfate
2. Og anhydrous potassium carbonate
37,5. Brominated “trium”
1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g
Potassium hydroxide 1. Add Og water
and set it to 11. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt +00. OB sex
Diamine diacetic acid diammonium salt 10. Og bromide
Ammonium +50. Og glacial acetic acid
Add 10.0wN water to 11
and using ammonia water, ρ11=6. Adjust to OI
Ru. [Fixer] Ammonium thiosulfate 175. Og anhydrous
Sodium sulfite 8.587 sulfite
Add 2.3g of sodium water and make 11.
and adjust the pH to 6.0 using acetic acid. [Stabilizer] Formalin (37% aqueous solution) 1, 5
+++1 Konigutsukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 7
．． Add 5 ml water to make 11. Relative sensitivity (S) and
Transmission sharpness (NTF) and RNS were measured. The result
It is shown in Table 1. Note that the relative sensitivity (S) is the exposure that gives a fog density of +0.1.
It is a relative value of the reciprocal of the light amount, and the W sensitivity of document N001 is set to 1.
It is shown as a value of 00. The sharpness improvement effect is due to the dye image
MTF (Modulation Transfer)
FuncLi. Find n) and find the relative value of MTF at 10 lines/111111
(Sample No. 1 is set as 100). Next, the sample before development was heated to 70°C, 45% R11.
Leave the specimen under these conditions for 3 days and observe the sweating phenomenon on the surface of the specimen using an optical microscope.
Observation was made using a mirror (magnification: 100). Although sweating phenomenon is observed
The result is (X) and the unacceptable one is (0).
are shown in Table 1. As shown in Table 1, the samples of the present invention have relative sensitivity, MT
It has a high F value and good sweating properties. Especially unsharp bon.
The image-forming compound has an effect on sharpness, but it has a soft ripple effect.
Synergistically enhanced in the presence of releasing compounds
I understand. that's all.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a coupling reaction of a fogging agent or a development accelerator or a precursor thereof with an oxidized form of a developing agent is carried out in at least one layer. 1. A negative-working silver halide photographic light-sensitive material, characterized in that it contains a compound emitted by the compound and a means for forming an unsharp positive image in combination with a layer containing the compound and/or a layer different from the layer.