JPH0660997B2 - Negative type silver halide photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a negative-type silver halide photographic light-sensitive material, and more specifically to a negative-type silver halide photographic light-sensitive material (hereinafter simply referred to as negative-type light-sensitive material) having improved image sharpness.

[Prior art]

In recent years, development of a color light-sensitive material having high sensitivity and improved sharpness has been strongly proposed. Conventionally, as a method for improving the sharpness, a method of reducing the thickness of the emulsion layer of a color light-sensitive material to minimize the light scattered by silver halide crystals in the emulsion layer, or a method of reducing the light in a certain spectral range Known is a method of improving sharpness by adding a substance (dye, UV-absorber) that absorbs unexposed light. To reduce the thickness of the emulsion layer, an oil-soluble component or gelatin can be prepared by polymer coupler technology described in JP-A-58-28745 or the like, or technology such as high-color color low-molecular weight coupler described in Japanese Patent Application No. 59-195234. However, the effect of improving the sharpness is not sufficient, and the effect of MTF (Modulotion Transfer Function) in the low frequency region is small. On the other hand, substances that absorb unwanted light in a certain spectral region are known by the concept of filter dyes and can be used directly in emulsion layers or in special filter layers of color light-sensitive materials. The place is divided into the following groups. (a) Layer Preventing Halation Due to Reflection This layer is always on the side of the emulsion layer opposite the exposed side, between the emulsion layer and the film base or on the back of the film base. The task of this layer is to pierce the emulsion layer downwards to avoid blurring of the image by so-called "halation by reflection" and to drive the gelatin-support or support-
It is to absorb the radiation reflected at the optical interface of air as completely as possible. Examples are German Patent Application Publication No. 2,
700,220. Therefore, the ideal color for this layer is black. That is, this layer should have a strong uniform absorption over the entire visible spectral region as much as possible. Although various realization possibilities are known, photographic materials always have only one layer which prevents halation by reflection. (b) In order to absorb the light scattered by the silver halide crystals and prevent so-called "scattering halation" from occurring, in this case a filter dye is added directly to the emulsion. The dyeing is commensurate with the sensitivity of the respective layers and causes a considerable loss of sensitivity and gradation. It is possible that one color light-sensitive material contains several kinds of dyes. (c) Filter intermediate layer of multilayer light-sensitive material This layer is useful for improving color reproduction and sharpness.
From the exposure side, this layer is always below the layer whose sharpness is to be improved, so that it acts as a layer to prevent halation by reflection in the sense of (a) and also the halogenation of the emulsion layer below it. It acts as a protective layer against the light scattered back by the silver crystals, thereby helping to reduce halation due to scattering. At the same time, this layer improves the color reproduction of the underlying emulsion layer by preventing undesired exposures in the spectral region outside the sensitivity region provided for the recording of information. Therefore, the filter interlayer must absorb as much light as possible in this region of the detrimental secondary sensitivity, but the highest sensitivity of the emulsion layer below the filter layer as seen from the exposure side is present. It should not absorb light in the spectral region that An important example is the yellow filter layer of a color light-sensitive material that corrects the unwanted blue sensitivity of emulsion layers sensitized for green or red light. Another example is the red intermediate layer between the green-sensitive layer and the red-sensitive layer of a color light-sensitive material, such as those mentioned in DE-A 2,453,217. It is explicitly pointed out here that for red light (the layer underneath the filter layer is sensitized to red light) a maximum transmission is required. Similar examples are contained in DE-A 2,711,220. A single color light-sensitive material may have several intermediate layers. Although the above method improves sharpness, the degree of improvement is still not sufficient. On the other hand, a technique is known in which an unsharp positive image is combined with a negative image to enhance the boundary portion (edge portion) of the image and improve the apparent sharpness. Introduce the sensitivity and loss of gradation. As another sharpness improving technique, it is known that the sharpness is improved by using a development inhibitor or a DIR compound that releases a precursor thereof by reacting with an oxidized product of a color developing agent, The improvement effect of MTF in the high frequency region is small, and there is a loss of sensitivity and gradation, so it is not at a sufficient level.

[Object of the Invention]

An object of the present invention is to provide a negative type silver halide photographic light-sensitive material having excellent sharpness, sensitivity and gradation.

[Constitution of the invention]

 As a result of earnest studies, the present inventor has found that the photosensitive halo on the support is
At least one of the silver genide emulsion layers is represented by the following general formula.
Contains a yellow coupler, and contains the puller.
Layer and / or a colorant having a different color sensitivity.
An unsharp positive image combined with a silver halide emulsion layer
Negative halo characterized by containing a means for forming
Achieved the above objectives by using silver photographic material
I found that I would be done. General formula [1]Where R¹, R^TwoAnd R^ThreeMay be the same or different,
Hydrogen atom and halogen atom (eg fluorine, chlorine, odor)
Each atom of element, etc.), alkyl group (eg methyl, ethyl,
Groups such as allyl and dodecyl), aryl groups (eg
Each group such as nyl and naphthyl), an alkoxy group (for example, meth)
Groups such as key, ethoxy, dodecyloxy), acyl
Mino groups (eg acetamide, α (p-dodecyloxy
Phenoxy) butanamide and other groups), carbamoyl groups
(For example, carbamoyl, N, N-dimethylcarbamoy
N, δ- (2.4-di-tert-amylphenoki
Si), each group such as butylcarbamoyl), and alkoxycarl
Bonyl groups (eg ethoxycarbonyl, dodecyloxy
Carbonyl, α (dodecyloxycarbonyl) etoki
Each group such as cycarbonyl), sulfonamide group (for example,
Methanesulfonamide, p-dodecyloxybenzenes
Rufonamide, N-benzyldodecanesulfonamide, etc.
Each group), or a sulfamoyl group (eg, sulfamo)
, N-methylsulfamoyl, N-δ- (2.4-
Di-tert-amylphenoxy) butylsulfamoyl,
Each group such as N, N-diethylsulfamoyl). R^Four, R⁵, R⁶And R⁷May be the same or different,
Hydrogen atom, alkyl group (eg methyl, ethyl, te
rt-butyl etc.), alkoxy groups (eg methoxy groups)
Si, ethoxy, propoxy, octoxy, etc.), a
Reeloxy group (eg phenoxymethylphenoxy etc.
Each group), an acylamino group (for example, acetamide, α-
(2.4-Di-tert-amylphenoxy) butanamide
Etc.) or a sulfonamide group (eg methanesulfur)
Honamide, p-dodecylbenzenesulfonamide, N
-Each group such as benzyldodecanesulfonamide). W is a halogen atom (eg, fluorine atom, chlorine atom, bromine)
Atoms, etc.), alkyl groups (eg methyl, ethyl)
Group, such as tert-butyl, tert-butyl), and an alkoxy group (for example,
Toxy, ethoxy, propoxy, octoxy, etc.
Groups), aryloxy groups (eg phenoxy, methylphenyl)
Groups such as enoxy) or dialkylamino groups (eg,
Dimethylamino, N-butyl-N-actylamino, etc.
Represents each group). X represents a hydrogen atom or a removable group. That is, according to the research by the present inventor, the general formula [1] of the present invention
When the compound represented by
It is possible, and some improvement in sharpness is recognized, but MT
The effect of improving F in the low frequency range is small. Also, this compound
Has almost no effect on sensitivity and gradation.
won. On the other hand, the unsharp positive image of the present invention is formed.
The edge effect is emphasized in the sensitive material using the means
However, it causes remarkable desensitization and softening. However,
According to the combination of the present invention, the improvement of the MTF in the entire frequency range
The sharpness is greatly improved and
For desensitization and softening development by forming a sharp positive image
Finds the surprising fact that it can be extremely small
It was That is, the combination of the present invention provides excellent sharpness and
Achieved the purpose of providing negative type photosensitive material with excellent degree and gradation
Was done. Next, the coupler of the present invention will be described. Yellow dye image type represented by the general formula [1] of the present invention
A product coupler can be preferably used. General formula [1]Where R¹, R^TwoAnd R^ThreeMay be the same or different,
Hydrogen atom and halogen atom (eg fluorine, chlorine, odor)
Each atom of element, etc.), alkyl group (eg methyl, ethyl,
Groups such as allyl and dodecyl), aryl groups (eg
Each group such as nyl and naphthyl), an alkoxy group (for example, meth)
Groups such as key, ethoxy, dodecyloxy), acyl
Mino groups (eg acetamide, α (p-dodecyloxy
Phenoxy) butanamide and other groups), carbamoyl groups
(For example, carbamoyl, N, N-dimethylcarbamoy
Le, N-δ- (2.4-g-tert-amylphenoki
Si), each group such as butylcarbamoyl), and alkoxycarl
Bonyl groups (eg ethoxycarbonyl, dodecyloxy
Carbonyl, α (dodecyloxycarbonyl) ethoxy
Each group such as carbonyl), sulfonamide group (for example, meta
Sulfonamide, p-dodecyloxybenzenesulfon
Namide, N-benzyldodecanesulfonamide, etc.
Group), or a sulfamoyl group (eg, sulfamoyl
, N-methylsulfamoyl, N-δ- (2.4-di
-Teft-amylphenoxy) butylsulfamoyl,
Each group such as N, N-diethylsulfamoyl). R^Four, R⁵, R⁶And R⁷May be the same or different,
Hydrogen atom, alkyl group (eg methyl, ethyl, te
rt-butyl etc.), alkoxy groups (eg methoxy groups)
Si, ethoxy, propoxy, octoxy, etc.), a
Reeloxy group (eg phenoxymethylphenoxy etc.
Each group), an acylamino group (for example, acetamide, α-
(2.4-Di-tert-amylphenoxy) butanamide
Etc.) or a sulfonamide group (eg methanesulfur)
Honamide, p-dodecylbenzenesulfonamide, N
-Each group such as benzyldodecanesulfonamide). W is a halogen atom (eg, fluorine atom, chlorine atom, bromine)
Atoms, etc.), alkyl groups (eg methyl, ethyl)
Group, such as tert-butyl, tert-butyl), and an alkoxy group (for example,
Toxy, ethoxy, propoxy, octoxy, etc.
Groups), aryloxy groups (eg phenoxy, methylphenyl)
Groups such as enoxy) or dialkylamino groups (eg,
Dimethylamino, N-butyl-N-octylamino, etc.
Represents each group). X represents a hydrogen atom or a removable group. With a removable group
A preferred group is represented by the general formula [2]. General formula [2]Y represents a group of non-metal atoms necessary for forming a 5- or 6-membered ring.
You (The cyclic compound formed is, for example, 25-dioxo.
-Imidalin, 2,5-pyrrolidinedione, 1,3-a
Soindole dione, 2,3,5-trioxoimida
Zolidine, 2,5-dioxo-triazolidine, 2,4
-Oxazolidinedione, 2,4-thiazolidinedio
2 (1H) -pyridone, 2 (1H) -pyrimidone, 2 (1H) bi
Razone, 5 (1H) -imidazolone, 5 (1H) -triazolo
2 (1H) -Bilimidone, 2-pyrazolone (5), 2-a
Sothiazolone (5), 2 (1H) -quinoxazolone, 4 (3H)
-Pyrimidone, 2-benzoxazolone, 4-isooxy
Sazolone (5), 3-Fluorone (2), 4-Imidazolone
(2), 3-pyrazolone, 2-tetrazolone (5), 3-teto
Represents each derivative such as razolone (5). ) The components of the yellow coupler represented by the general formula [1] are shown below.
Here are some examples. It is also preferable as a means for forming an unsharp positive image
As a color negative image containing a diffusion resistant coupler
Ansher combined with a forming silver halide emulsion layer
Positive image forming compound (hereinafter referred to as positive compound)
Can be mentioned. One preferable example of the positive compound is small diffusibility, and
Diffusivity-resistant coupler for color reaction in reaction with oxidant of main agent
The main absorption wave of the resulting dye (hereinafter referred to as the coloring dye)
Colored compound with main absorption in the long range or during development processing
Is a so-called precursor that is a compound that changes color to the colored compound.
The color of the developing agent as a result of reaction with the oxidant of the developing agent.
A diffusion-resistant dye that has a main absorption in the main absorption wavelength range of the element
Compound generated (hereinafter referred to as small diffusible positive compound)
Is. Another example of a positive compound is diffusion resistance.
Yes, having a main absorption in the main absorption wavelength range of the coloring dye
Color compounds or compounds that change color to the colored compounds during development processing
Of a developing agent, resulting in decolorization as a result of reaction with the oxidant of the developing agent.
Compound (hereinafter referred to as a diffusion resistant positive compound).
It The small diffusible positive compound will be described in detail. What is small diffusivity during 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 treatment process
At least 30 wt% of the amount remains in the photographic material
Say that. As for the degree of discoloration, the change in maximum absorption wavelength is 10 nm or less.
The above is preferable. As such a color change mechanism,
Color tone changes due to hydrolysis of di-compound
Preferred are those mentioned above. Decoloring means that a colored compound is not produced or
The formed colored compound flows out of the photographic material during development processing.
At the end of the drawing process, the unsharp positive
Colored compounds remain in the photographic material to the extent that they impair image formation.
It means not staying. Such a decolorizable small diffusible positive compound is combined with a color developing agent.
The area where a color image is produced by the reaction with the diffusion resistant coupler.
In the area, it reacts with the oxidant of the developing agent to erase the color. Also resistant
Unreacted in areas where color images due to diffusive couplers do not occur
Or, it remains in a discolored state. As a result, diffusion resistance
Reversed color image by puller and decolorizable small diffusive positive compound
The color image of interest, i.e. the former is used to form the negative image.
However, the latter forms a positive image. Moreover, small
Since the diffusible positive compound has a small diffusivity,
Form a sharp image, that is, an unsharp positive image
Will be done. Next, as a result of the reaction with the oxidant of the developing agent,
Produces anti-diffusive dyes that have the main absorption in the absorption wavelength range
Type of small diffusible positive compound, that is, small type of diffusive dye-forming type
The diffusible positive compound will be described. Diffusion-resistant dye-forming small diffusive positive compounds are diffusion-resistant caps.
Unreacted or discolored in areas where color images do not occur
To do. As a result, the color image produced by the diffusion-resistant coupler is
A color image that is inversely related to a small diffusible positive compound that has undergone a color change or discoloration.
Image, that is, if the former is a negative image, the latter is a positive image.
Will be formed. Moreover, the small diffusive positive compounds are small
Due to its dispersiveness, it provides an unsharp image
Then, an unsharp positive image is formed. The diffusion resistant dye-forming type small diffusible positive compound is as described above.
In addition to forming an unsharp positive image, a developing agent
Due to the reaction with the oxidant of
This produces a diffusion resistant dye that has a barrel absorption. This anti-diffusion
Dyes are the above-mentioned diffusion-resistant couplers and the oxidation of color developing agents.
Colored together with diffusion-resistant dyes that are generated by reaction with the body
Form an image. This diffusion resistant dye forming type small diffusive positive compound is as described above.
And an unsharp positive image and a diffusion-resistant dye
Produces both moth images. Therefore, both images overlap and
In some cases, it may not appear that the concentration changes.
However, at the edge (the boundary where the intensity of the light changes),
Due to the difference in the diffusivity of the positive compound and the produced diffusion resistant dye
Causes more microscopic density changes (edge effect)
Is effective as an unsharp positive image forming means.
is there. Examples of the decolorizable small diffusible positive compound include the following general
Examples include compounds represented by the formula [1]. General formula [1]
A-Link-B In the formula, A reacts with the oxidized product of the developing agent and the Link-B portion is
Organic residue that can be released according to the amount of oxidized developer
, Link is a group that connects A and B, and B is a free residue.
You In addition, the compound represented by the general formula [1] is used during the development process.
It is a colored or discolored compound that diffuses in crab photographic materials.
There is a product generated due to A and Link-B after the reaction.
In the case of a colored compound, the product is reacted in the photographic material after reaction.
Balance the hydrophilicity or lipophilicity so that it flows out of the system more
The substituents taken are attached. Examples of A in the general formula [I] include, for example, color developing agents.
Colored or colorless product by coupling reaction with oxidant of
Cross-linking with the residue of the coupler or the oxidant of the developing agent
Examples include components that undergo an oxidation reaction. Specific examples of the former include, for example, phenols and naphtho
, 5-virazolones, virazocotriazoles,
Pyrazolobenzimidazoles, indazolones, reeds
Luacetanilides, R₈COCH₃(R₈Is, for example, Archi
Group, aryl, heterocyclic group)(Z is, for example, a 5- to 8-membered saturated or unsaturated alicyclic ring or
R is an atomic group that completes a heterocycle.₉Indicates an aryl residue
You ) Residue. Specific examples of the latter include, for example, an alkali after being oxidized.
B-SO as Link-B by cleavage₂Hueno releasing NH
, Naphthols, indanones, indoles,
Residue of hydroquinone, after oxidation, intramolecular ring closure
In response, B-SO as Link-B₂Emitting feno
(See U.S. Pat. Nos. 3,443,939 and 3,443,940 for details.
No. 3,443,941. ) Residue
To be As the Link, for example, -N = -N-,-O-,-S-,-NH-SO
₂-,-SO₂-NHH-,-CH = and the like. here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl imidazole
Zolonyl, Benzimidazolyl, Hydantoyl, Thio
Hydantoyl, triazolyl, benztriazolyl, u
Razolyl, 2,4-dioxyoxazolyl, 2,4-di
Oxo thiazolyl, thiadiazolyl, tetrazolyl
and so on. Also, R_TenMay each have a substituent
Alkyl, aryl and the like. As B, Link is a chromophore such as -N = N-, -CH =
In the case, for example, an aryl group or a heterocyclic group, preferably
Is a dye residue even if it is an organic residue having an auxochrome
Good. Also, if the Link is not a chromophore, a dye (eg
For example, azo, anthraquinone, azomethine, indopheno
, Indoaniline, etc.) residues are preferred.
The compound represented by the general formula [1] having the above structure is B
Coloring or discoloring the part or the entire A-Link-B
It can be a combination. The compound represented by the general formula [1] is slightly spread during development processing.
Dispersible properties and undesired formation after reaction
For example, to add the diffusivity to let things flow out of the system,
For example, carboxyl group, sulfo group, hydroxyl group, sulf
Alkali-soluble groups such as amoyl groups and, for example, alkyl groups.
Reaction by appropriately introducing a group that reduces diffusivity such as
It suffices to balance the front and rear diffusion properties. The compounds of the present invention are classified according to their properties.
The classification is as follows. CLASSI: Coloring dye forming type In the compounds belonging to this class, the A part of the general formula [I] is
The Link part binds to the active site of the coupler at the puller residue. However
And Link-NHSO₂-In case of (bonding of nitrogen atom in Coup part)
In this case, it may be adjacent to the active point. And, in the photographic material, it is preferable to use an alkali so as to diffuse a small amount
It has a re-soluble group and, for example, an alkyl group having 16 or less carbon atoms.
To do. Part A couples with the oxidant of the color developing agent
To give a colored compound, the compound may be added to the system during processing.
Alkali-soluble group is present in the A part so that it will flow out.
It has an alkali-soluble group as a color developing agent.
Is preferably used. When the B portion forms a dye, the B portion after the reaction
The portion B has an alkali-soluble group so that it may flow out of the system.
It is preferable that For the compounds belonging to this category, the A part in the exposed area develops a negative color.
When a dye image is formed but flows out of the system, and part B is a dye
In addition, the B part also flows out of the system after leaving the A part.
And the compound represented by the general formula [1] which remains in the unexposed area or
Make a positive image with the compound after the color change. Besides, this compound
Since the material has a small diffusivity, it does not pass through the layers during development processing.
To the unsharp positive image. More
The following two types are preferred among these types:
The following are listed. (Type A): Colored coupler type General formula [II] Coup-Link₂-Ar Coup- in the general formula [II] is a coupler residue and is alkali-soluble.
It is preferable to have a group, the color generated by the color development reaction.
The element flows out of the photographic material system. Ar is an aryl group which may have a substituent, for example, benzene.
-Based or naphthalene-based and optionally substituted heterocycles
Groups such as isoxazole are preferred and
The compound of general formula [II] migrates slightly in the photographic material.
Therefore, it preferably has a semi-diffusion preventing group, especially in the Ar part.
Is preferred. Link₂Is -N = N- or -CH =. This
Some of these compounds are already colored couplers, for example
For example, U.S. Patent Nos. 2,449,969, 2,688,538, and 2,706,
684, 2,808,329, 3,005,712, Belgian Patent 5
It is known for 70,271 and Japanese Patent Publication No.44-32461. However, in the present invention and these prior arts, the usage of compounds is
The purpose is different, and the effect obtained is
It is completely foreign. That is, the prior art is
By the coup portion or coupler portion represented by the formula [II]
This part is because the resulting hue is the main absorption that forms the image.
In principle, the dye generated from
The hue of the compound represented by [II] is different from the main absorption wavelength range.
It is the secondary absorption part. The invention originates from the Coup part
It is essential that the dye be taken out of the system, and the general formula [I
The hue of the compound represented by [I] or the compound after discoloration is
This is the same as the main absorption of the image forming layer. That is, the compound of the present invention
The photosensitive wavelength range of the silver halide layer combined with
Compound color if conventional negative photographic material
It is the complementary color of the phase. Specifically, for example, with a green-sensitive negative layer
To explain, prior art colored couplers have yellow layers in this layer.
In the present invention, a magenta color or
A compound that changes color to magenta is used. (Type B): Active site replacement type General formula [III] Coup-Link₃-Dye Coup is the same as the general formula [II]. Also, Link₃Is the general formula
It is synonymous with Link of [I] and similar ones are illustrated and
More preferably, it becomes alkali-soluble after the coupling reaction
Groups such as -O-, -SO₂-NH-, -NHSO₂-And so on
Good Dye represents a dye portion or a dye precursor portion, and
It is desirable to have Lucari soluble group, but Link₃Type of
Not required by some. The compound represented by the general formula [III] is slightly contained in the photographic material.
In order to adjust the diffusion of
And are preferred. The group is a coloring dye and Link₃-Dye has good diffusion
It is preferable to attach to the above. It belongs to this kind of classification
Examples of the compound include U.S. Patent Nos. 3,227,550 and 3,476,563.
However, these prior arts are the same as Type A.
Is completely different in usage and does not include the concept of the present invention.
Absent. That is, some of them are the same as the type A color couplers.
When it is used correctly, Dye part that diffuses and transfers and flows out
Is clearly different from the embodiment of the present invention in the case of using
ing. Next, we will explain the compounds that do not produce a color image after the color reaction.
Reveal CLASSII: colorless coupling body-forming type Compounds belonging to this class are CALS in the A part of general formula [I].
Reacts like SI 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-Link_Four-For Dye Wcoup, for example, R₁₁COCH₂-(R₁₁Is Archi
Alkyl groups having 16 or less carbon atoms with
Hold),(Z completes a 5- to 8-membered alicyclic ring, condensed ring or heterocyclic ring
R in the atomic group₁₂Represents an aryl residue. ). Link_FourIs -O-, -S- or -SO₂-Indicates. Dye is a dye residue or preferably having an alkali-soluble group.
Is its precursor part and Link_Four-Dye flows out of the layer. Also, this compound is an alkali that may be present in the Dye part.
The compound itself diffuses slightly through the layer in cooperation with soluble groups
Therefore, it is preferable that the
Preferably in the W-coup part. CLASSIII: Redox reaction type Compounds belonging to this class are CLASS I or II-like compounds.
Ring reaction is not performed. Instead, it reacts with the oxidized product of the developing agent.
To produce quinone, quinimide, etc.
React with the alkali in the developer or undergo an intramolecular ring closure reaction
Releases dye for the first time. (TypeD): DRR compound type General formula [V] FUN-Link_Five-Dye FUN indicates a redox mother nucleus and is 2-, 3- or 4-phenotype.
Nole, 4-α-naphthol, 1-β-naphthol, 2
-Hydroquinone, 3-indole, 4-pyrazolone-
5 residues, Link_FiveIs -NHSO₂-(Nitrogen atom is FUN part
, -O-, -SO_Two-, -S-, etc., and Dy
e is a dye residue or its precursor part, soluble in alkali
It is preferable to have a functional group. So that the compound of the general formula [V] diffuses slightly in the layer.
Alkali-soluble group that may be present in the Dye part
When using a semi-diffusion prevention group that cooperates with, attach it to the FUN part
Preferably. As described above, the diffusion-resistant dye-forming type small diffusible compound is
A color developing agent as well as a dye or its precursor
That produces a diffusion-resistant dye by reaction with the oxidant of
However, due to the reaction, a new dye portion is formed.
May be used, or a new dye part is not formed and
The dye portion or its precursor portion before the development process
After that, it remains as the dye part of the diffusion resistant dye.
May be. As a diffusion-resistant dye-forming small diffusible compound,
From the following types. Pre-existing by coupling with type I color developing agent oxidant
The dye part or its precursor that is present during the development process
A new pigment portion that is substantially the same color as the sly pigment portion is newly generated.
At the same time, it is a compound that is resistant to diffusion (dye-forming type). This type is described in more detail below.
Can be similar. A type I-1 color developing agent that has a color developing agent in advance by coupling with an oxidant.
The dye portion or its precursor portion is decolored and
The dye portion or its precursor portion is present after the development processing step.
Should form a pigment part that is substantially the same color as the pigment
A compound that is resistant to diffusion. Type I-2 Pre-existing by coupling with oxidant of color developing agent
The dyed part or its precursor part is not erased.
In addition, the dye portion or the precursor portion is newly developed.
A dye part that has substantially the same color as the dye part that should be produced after the process
A compound that forms and resists diffusion. So this type
As a result of coupling with the oxidant of the developing agent,
Dye portion that is already present or dye portion derived from its precursor
In addition to the newly formed dye portion, diffusion resistance
It produces a pigment (additional type). Pre-existing by coupling with oxidant of type II color developing agent
The dyed part or its precursor part is not erased.
Diffusion resistance without forming new dye parts
Compound. Cross-oxidation of type III color developing agents with oxidants
A compound that is resistant to diffusion. Each of the above types will be described in more detail. Examples of the compound of Tap I-1 include compounds represented by the following general formula [I-
1] are mentioned. General formula [I-1] A₁-Link₂-B₁ A in the formula₁Is coupled to the oxidized form of the developing agent and is Link-B
₁When the part is released according to the amount of the oxidized product of the developing agent,
An organic residue capable of forming a coupling dye,
Link₁Is A₁And B₁A group that binds to B₁Represents an organic residue
Forget A₁As specific examples of, for example, phenols, naphtho
, 5-pyrazolones, pyrazolotriazoles,
Pyrazolotetrazole, Pyrazolobenzimidazole
, Indazolones, acylacetanilides, etc.
You can Link₁Examples of the amide include -N = N-, -O-,-
S-, -SO₂,And so on. here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl, imi
Dazolone il, Benzimidazolyl, Hydantoyl, Chi
Ohydantoyl, triazolyl, benztriazolyl,
Urazolyl, 2,4-dioxyoxazolyl, 2,4-
Dioxothiazolyl, thiadiazolyl, tetrazolly
There are such as Le. B₁As a Link₁Is a chromophore such as -N = N-
Is preferably, for example, an aryl group or a heterocyclic group, and Li is
nk₁Is not a chromophore, a dye (eg, azo, an
Traquinone, azomethine, indophenol, indoor
Nilin, etc.) residue or its precursor is preferred.
Yes. The compound represented by the general formula [I-1] having the above structure
Thing, B₁Or A₁-Link₁-B₁Pigment or as a whole
It may be its precursor. The compound represented by the general formula [I-1] was added to the compound during the development process.
Adds the property of diffusing quietly, B₁Is a dye or its precursor
In the case of the body, the pigments caused by these flow out of the system.
Diffusion resistance of dye generated by coupling
For example, carboxyl groups, sulfo groups, hydroxy groups
Alkali-soluble groups such as sil and sulfamoyl groups
And a group that reduces diffusibility, such as an alkyl group,
Introduce it appropriately to balance the diffusivity before and after the reaction.
Yes. Examples of the compound of type I-2 include compounds represented by the following general formula [I
-2]. General formula [I-2] D₁-A_Two In the formula, D₁Represents a dye portion or a precursor portion thereof, and A_Two
Couple with the oxidant of the developing agent to form a dye
Represents an organic residue, but D₁Is A for coupling
_TwoNever leave. A_TwoAs a concrete example of₁Shown as a specific example of
There are things. D₁As an example of₁Dye residues listed as examples
And precursors thereof. See A_TwoIs the coupling position
Even if it has a group that can be released during coupling
Good. The releasable group may be a dye or its precursor
Good, but not necessarily a dye or its precursor
Yes. Further, the compound represented by the general formula [I-2] is not processed during development.
It has the property of gently diffusing and has the general formula [I-2].
As a result of the coupling of the compound with the oxidant of the developing agent.
To make the chewy dye resistant to diffusion, for example, carboxyl
Group, sulfo group, hydroxyl group, sulfamoyl group
Alkali-soluble groups and diffusion such as alkyl groups
By introducing a group that decreases the
Just balance. For example, A_TwoAt the coupling position of
Releasable alkali-soluble group or alkali-soluble group
It is also possible to bond a group containing As the compound of type II, for example, the following general formula [II-
1] are mentioned. General formula [II-1] WD_Two In the formula, D_TwoIs D in the general formula [I-2]₁Synonymously
The same thing is illustrated. W is a cup that couples with the oxidant of the developing agent
Compound residues that do not form a dye due to the ring
Represents Examples of W include 5-pyrazolone nucleus and β-diketometh
Coupling at the coupling position of the coupler residue such as
Reaction (eg, oxidation reaction,
Groups that do not cause elimination reactions (eg methyl group, butyl group)
Substituted with alkyl groups such as
Vamoyl-areoxymethane series or bisalkyl carbonate
Luvamoyl-aryl thiomethane-based compound residues include
To be In the general formula [II-1], D_TwoIs the coupling position of W
As a part of the group that does not cause the reaction to transfer to the dye
May be present at a position other than the coupling position.
May be combined with. As the compound of type III, for example, the following general formula [III-
1] are included. General formula [III-1] Fun-D_Three In the formula, D_ThreeIs D in the general formula [I-2]₁Synonymous with
The same thing is illustrated. Fun reacts with the oxidant of the color developing agent and has the general formula [III-
[1] An organic group having a function of making a compound resistant to diffusion
A group having a hydroquinone nucleus and a catechol nucleus
Group. Next, the diffusion resistant positive compound will be described in detail. Here, for decoloring and discoloring, a small diffusible positive compound
, Are synonymous with them. The reaction between the oxidation product of the color developing agent and the diffusion resistant coupler
Diffuse resistant positive compounds are also the main developer
Compound that reacts with the oxidant of the drug and becomes colorless or elutes outside the system
Or either characteristic is expressed. Also, diffusion resistant
Diffusion resistant porosity in areas where color images are not produced by
Di-compound remains unreacted or discolored
It As a result, diffusion resistant couplers and diffusion resistant positive compounds
In the case of a negative color image, that is, when the former is a negative image
The latter will form a positive image. Moreover, diffusion resistance
Positive compound from the layer containing the diffusion resistant coupler
Oxidizing agent for developing agent diffuses and diffuses positive compound
Unsharp image by reaching the layer containing
Image, that is, to form an unsharp positive image.
It As the diffusion resistant positive compound, for example, the following general formula [A-
1] are mentioned. General formula [A-1] A_Three-Link-B_Three A in the formula_ThreeReacts with the oxidant of the developing agent, Link-B_ThreePart
Can be colorless or eluted depending on the amount of the above-mentioned oxidized form of developing agent
Link is A_ThreeAnd B_ThreeCombine
Base, B_ThreeRepresents an organic residue. Further, the compound represented by the general formula [A-1] is used during the development processing.
Diffuse-resistant colored or discolored compound in photographic materials
Yes, after reaction A_ThreeAnd Link-B_ThreeGenerated due to
When the object is a compound that shows an unsuitable hue for image formation
After the reaction of the product,
Balanced hydrophilic or lipophilic so that it elutes to the outside
Substituents are attached. A in the general formula [A-1]_ThreeFor example,
Colored or colorless by coupling reaction with the oxidant of the image base
With the residue of the coupler that produces the product or the oxidized form of the developing agent
Examples include components that undergo a cross-oxidation reaction. Specific examples of the former include, for example, phenols and naphtho
, 5-pyrazolones, pyrazolotriazoles,
Pyrazolobenzimidazoles, indazolones, reeds
Luacetanilides, R₈COCH₃(R₈Is, for example, Archi
Group, aryl, heterocyclic group)(Z is, for example, a 5- to 8-membered saturated or unsaturated alicyclic ring or
R is an atomic group that completes a heterocycle.₉Indicates an aryl residue
You ) Residue. Specific examples of the latter include, for example, an alkali after being oxidized.
B-SO as Link-B by cleavage₂Feno releasing NH
Of naphthols, naphthols, indanones and indoles
Residues are oxidized and alkali-cleaved to form Link-B
, B-O, B-S, B-SO₂Hydroquino that emits
After being oxidized, they undergo an intramolecular ring closure reaction,
B-SO as nk-B₂Releasing phenols (details
Are U.S. Patent Nos. 3,443,939, 3,443,940 and 3,443,94.
It is described in No. 1. ) Residue. As the Link, for example, -N = N-, -O-, -S-, -S
O₂−, −NH−SO₂−, −SO₂-NH-,-CH = and the like. here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl, imi
Dazolone il, Benzimidazolyl, Hydantoyl, Chi
Ohydantoyl, triazolyl, benztriazolyl,
Urazolyl, 2,4-dioxyoxazolyl, 2,4-
Dioxothiazolyl, thiadiazolyl, tetrazolly
There are such as Le. Also, R₁₀Each has a substituent
Good alkyl, aryl and the like. As B, Link is a chromophore such as -N = N-, -CH =
In the case, for example, an aryl group or a heterocyclic group, preferably
Is a dye residue even if it is an organic residue having an auxochrome
Good. Also, if the Link is not a chromophore, a dye (eg
For example, azo, anthraquinone, azomethine, indopheno
, Indoaniline, etc.) residue or its precursor
It is preferable. With such a structure, in the general formula [A-1]
The compound shown is B_ThreePart or A_Three-Link-B_Threeall
It may be a compound that is colored or discolored as a body. Diffuses in the compound represented by the general formula [A-1] during development processing.
Undesired product after the reaction
To impart diffusivity for elution to the outside of the system, for example,
Carboxyl group, sulfo group, hydroxyl group, sulfa
Alkali-soluble groups such as moyl groups and, for example, alkyl
Before the reaction by appropriately introducing a group such as a group that reduces diffusivity
It is sufficient to balance the diffusibility afterwards. The compounds of the present invention are classified according to their properties.
The classification is as follows. CLASSI: Coloring dye forming type Compounds belonging to this class are A of the general formula [A-1]._ThreeDepartment
Min is the coupler residue and the Link part binds to the active point of the coupler.
It However, A_ThreePhenol residue or naphthol residue
Base, Link is -NHSO₂-(Nitrogen atom is the bond of Coup part
In the case of), it may be adjacent to the active site. That
, Ballast groups, for example, to have resistance to diffusion in photographic materials
For example, it has an alkyl group having 17 or more carbon atoms. A_ThreePart fired
Coloring dye formed by coupling with oxidant of color developing agent
Is not suitable for image formation, the coloring dye
A that will be washed away from the system_ThreeAlkali-soluble group exists in the part
It has an alkali-soluble group as a color developing agent.
It is preferable to use one that does. Also, B_ThreeWhen a part forms a dye or its precursor
In case of B after reaction_ThreeB so that the part flows out of the system_Threepart
Preferably has an alkali-soluble group. Compounds belonging to this category are A_ThreePart is negative
A colored dye image is made, but it is washed away from the system and B_ThreePart is pigment
In case of_ThreePart A_ThreeAfter leaving the part, flow out of the system
It is lost by the general formula [A-1] that remains in the unexposed area.
Compound or its discolored compound creates a positive image.
It Moreover, the periphery of the positive image due to this compound is diffused
During the development process due to the reaction with the oxidant of the developing agent
An unsharp positive image is formed in the layer. Furthermore this kind of
Among them, the following two types are preferable.
Is mentioned. (TypeA): Colored coupler type General formula [A-2] Coup-Link²-Ar Coup- in the general formula [A-2] is a coupler residue and can be an alkali.
Having a soluble group is preferred
Dyes are eluted outside the photographic material system. Ar is an aryl group which may have a substituent, for example, benzene.
-Based or naphthalene-based and optionally substituted heterocycles
Groups such as isoxazole are preferred and are also generally
The compound of formula [A-2] spreads so as not to diffuse in the photographic material.
It has an anti-dispersing group, and it is particularly preferable to have it in the Ar part. Link
²Is a chromophore, preferably -N = N- or -CH =.
Some of these compounds are already colored couplers,
For example, U.S. Patent Nos. 2,449,966, 2,688,538 and 2,70
No. 6,684, No. 2,808,329, No. 3,005,712, Japanese Patent Publication No.44-32
It is known as No. 461. However, in the present invention and these prior arts, the usage of compounds is
The purpose is different, and the effect obtained is
It is completely foreign. That is, the prior art is
By the Coup portion, ie, the coupler portion, represented by the formula [A-2],
This is because the hue that is generated is the main absorption that forms the image.
In principle, the pigment generated from the part does not move, and it is generally
The hue of the compound represented by the formula [A-2] is the above main absorption wavelength.
It is a secondary absorption part that is different from the region. From the Coup part
It is essential that the resulting dye be taken out of the system, and
The hue of the compound represented by the formula [A-2] is the same as that of the image forming layer.
It is the same as the main absorption. That is, the compound of the general formula [A-2]
The photosensitive wavelength range of the silver halide layer combined with
Compound color if conventional negative photographic material
It is the complementary color of the phase. Specifically, for example, with a green-sensitive negative layer
To explain, prior art colored couplers have yellow layers in this layer.
In the present invention, a compound of magenta color is used, while a compound of color is used.
Are using things. (Type B): Active site replacement type general formula [A-3] Coup-Link³-Dye Coup is the same as in the general formula [A-2]. Also, Link³Is one
It has the same meaning as Link of general formula [A-1], and similar ones are examples.
And preferably alkali-soluble after the coupling reaction.
The resulting groups, such as -O-, -SO²-NH-, -NHSO₂− Etc.
Is desirable. Dye represents the dye moiety or its precursor moiety
However, it is desirable to have an alkali-soluble group, but Link³
Not required depending on the type of. It belongs to this kind of classification
The compounds to be used are U.S. Patent Nos. 3,227,550 and 3,476,563.
However, these prior arts are the same as Type A.
It is completely different in usage and includes the concept of the present invention.
Not in. That is, part of it is the same color as the Type A colored coupler
When it is used for correction and when it is diffused and transferred and Dye comes out
When a part is used for an image, it is clearly different from the embodiment of the present invention.
ing. Next, we will explain the compounds that do not produce a color image after the color reaction.
Reveal CLASSII: colorless coupling body-forming type Compounds belonging to this class are A of the general formula [A-1]._Threepart
Reacts similarly to CLASSI compounds, but the reaction product
Since it is colorless, even if it remains in the layer after the coupling reaction
Good. (TypeC): Weiss coupler type General formula [A-4] Wcoup-Link^Four-For Dye Wcoup, for example, R₁₁COCH₂-(R₁₁Is Archi
Group, aryl, or heterocyclic group. )(Z completes a 5- to 8-membered alicyclic ring, condensed ring or heterocyclic ring
R in the atomic group₁₂Represents an aryl residue. ). So
Then, the Wcoup part contains a compound represented by the general formula [A-4].
In order to make it resistant to diffusion, preferably a diffusion preventing group such as carbon number
It has 17 or more groups. Link^FourIs -O-, -S- or -SO₂-Indicates. Dye is preferably a dye having an alkali-soluble group, or
After reaction with the precursor residue Link^Four-Dye flows out of the layer. CLASSIII: Redox reaction type Compounds belonging to this class are cups such as CLASS I or II.
No ring reaction is performed. Instead, the developing agent oxidant and anti
Correspondingly, it produces quinone, quinimide, etc.
Substance reacts with alkali in the developer or undergoes intramolecular ring closure reaction.
Releases the dye for the first time. (TypeD): DRR compound type General formula [A-5] FUN-Link^Five-Dye FUN represents a redox nucleus, preferably 2-, 3- or
Is 4-phenol, 4-α-naphthol, 1-β-naphth
Tall, 2-hydroquinone, 3-indole, 4-pi
Razolone-5 residue, Link^FiveIs -NHSO₂− (Nitrogen atom
To the FUN part), -O-, -SO₂-, -S-, etc.
Dye is a precursor residue of dye and is soluble in alkali.
It is preferable to have a functional group. In addition, in the general formula [A-5]
The FUN part preferably diffuses so that the compound does not migrate through the layer
Has a blocking group. The above-mentioned positive compounds were synthesized according to general synthetic methods.
There are two main routes. That is, one
The dye portion is pre-synthesized and finally the dye portion is mixed with phosphorus oxychloride.
Or suitable acid chloride agent such as thionyl chloride
Therefore, use sulfochloride or acid chloride to replace the amino group.
Another synthetic method, which is a method of combining with other moieties that have
At the final stage, the dye moiety is attached by diazo coupling.
Is the way to get. In the case of a dye precursor, for example, after forming the dye, an auxiliary chromophore is added.
It can be obtained by acylation or the like. Positive compounds are halogen-containing compounds containing the aforementioned diffusion resistant couplers.
In the silver halide emulsion layer and / or separately from the silver halide emulsion layer
In the photographic constituent layers of. The other photographic constituent layer is adjacent to the silver halide emulsion layer.
It need not be a layer, but is preferably an adjacent layer,
Also, the positive compound itself is mainly in the main light-sensitive wavelength region of the emulsion layer.
The above silver halide emulsion layer
Position on the opposite side of the light incident side during exposure.
It is preferable in preventing the decrease in sensitivity. In addition, another picture above
The constituent layers have the same color sensitivity as the above photosensitive silver halide emulsion layer.
The photosensitive silver halide emulsion layer may be
It may be a photosensitive layer. In addition, diffusion-resistant positive compounds should be non-photosensitively contained.
And are preferred. When a positive compound is included in the non-photosensitive layer,
Of the developing agent generated by the development of the light-sensitive silver halide emulsion layer.
Of the oxidants, those that have diffused into the non-coupling layer
Reacts with a positive compound to form an unsharp positive image
Will be done. Use the positive compound in combination with the compound
0.01 to 1.00 mol per mol of diffusion resistant coupler
It is preferably 0.05 to 0.60 mol. Moreover, the addition
As the addition method, the same method as the diffusion resistant coupler described later is used.
Can be used. Next, another preferred embodiment of the present invention is as follows.
Is raised. One is the method of forming the unsharp positive image of the present invention.
The layer containing the step is yellow represented by the general formula [1].
Being closer to the support than the layer containing the coupler
preferable. On the other hand, the negative-working light-sensitive material of the present invention is coated on a support.
Red-sensitive layer containing Anne color coupler, magenta color coupler
A green-sensitive layer containing a puller and a yellow color-forming coupler.
It is preferably composed of a blue-sensitive layer. Furthermore
And preferably means for forming an unsharp positive image
The silver halide emulsion layers to be combined should have at least two
Particularly preferably, the halo is composed of layers of different degrees.
Low-sensitivity silver halide emulsion among silver genide emulsion layers, or
As described above, the unsharp layer is placed on the non-sensitive layer adjacent to it.
That is, it contains a means for forming a dicompound. Well
In another preferred embodiment, the negative impression of the present invention is
In the optical material, the totally hydrophilic colloid on the side having the emulsion layer
Total dry film thickness of the dry layer is 30 μm^TwoThe following is preferred
Yes. Here, the dry film thickness is the film thickness measured at 23 ° C and 55% humidity.
means. For the film thickness of each layer, see the cross section of the dried sample.
Measure the film thickness of each layer by enlarging the image with a scanning electron microscope.
It The dry film thickness of the entire hydrophilic colloid layer on the side having the emulsion layer
The lower limit of the total sum (hereinafter referred to as the thickness of the emulsion surface) is included.
Silver rogenide emulsion, oils such as couplers, additives, gelatin
There is a limit due to the volume occupied by binders such as
The thickness of the emulsion surface is preferably 5 μm and 30 μm, and more preferably
Is 10 μm and 24 μm. Particularly preferably, it is 10 to 20 μm.
is there. Next, in the present invention, the silver halide emulsion contains a halogen
Silver bromide, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, salt
Used in ordinary silver halide emulsions such as silver iodobromide and silver chloride.
Any of those used can be used, but especially bromination
It is preferably silver, silver iodobromide or silver chloroiodobromide. The silver halide grains used in the silver halide emulsion are acid
Obtained by either sex method, neutral method or ammonia method
But it's okay. The particles may be grown at one time, or seed particles
It may be grown after making. How to make seed particles and
The growth method may be the same or different. A silver halide emulsion has the same halide and silver ions.
Even if mixed occasionally, in the liquid in which one exists, the other
May be mixed. Also, the seaside growth of silver halide crystals
Considering the speed, the halide ion and silver ion
Sequential and simultaneous addition while controlling pH and pAg in the mixing pot
You may generate by doing. By this method,
Silver halide grains with a regular crystal form and a nearly uniform grain size
I have a child. Conversion at any step of AgX formation
Method may be used to change the halogen composition of the grains. During the growth of silver halide grains, ammonia and thioeth
Presence of known silver halide solvents such as phenol and thiourea
be able to. The silver halide grains can be formed by the process and / or formation of grains.
In the process of lengthening, cadmium salt, zinc acid, lead acid, tariu
Rhodium salt, iridium salt (including complex acid), rhodium salt (complex salt)
At least) and iron salts (including complex salts)
Also using one kind of metal ions, and
Alternatively, it is possible to add these metal elements to the particle surface.
Inside the particles by placing it in an appropriate reducing atmosphere.
Reduction sensitizing nuclei can be imparted to the surface and / or grain surface. After the growth of silver halide grains, the silver halide emulsion is
Unnecessary salts may be removed or
You can leave it alone. When removing the salts,
Search Disclosure (RD and below)
Abbreviation)
it can. Silver halide grains have uniform halogenation within the grains.
Even if it has a silver composition distribution, the inside of the grain and the surface layer
Even for core / shell grains having different silver halide compositions
Good. Silver halide grains are like cubes, tetrahedra and tetrahedra.
It may have a regular crystalline form, or it may be
It may have an irregular crystal form. These grains
Any ratio can be used for the {100} face and the {111} face in the child.
Can be used. Also, it may have a composite form of these crystal forms
Alternatively, particles of various crystal shapes may be mixed. The size of silver halide grains is 0.05 ~ 30μ, preferred
For example, 0.1 to 20 μm can be used. Silver halide emulsions have any grain size distribution
May be used. Emulsions with a wide grain size distribution
Disperse emulsion) may be used, and the grain size distribution
Narrow emulsion (called monodisperse emulsion. Monodisperse milk here
An agent is the standard deviation of the particle size distribution divided by the average particle size.
The value is 0.20 or less. Here the particle size is spherical
In the case of silver halide, the diameter should be
In the case of particles, the projected image is converted into a circle image of the same area.
Indicates the diameter of the mushroom. ) May be used alone or in combination of several kinds.
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. Silver halide emulsions are two or more types of halogen
The silver halide emulsion may be mixed and used. The silver halide emulsion can be chemically sensitized by a conventional method.
Wear. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
Noble metal sensitization method using gold or other noble metal compounds
It can be used alone or in combination. Silver halide emulsions are sensitizing dyes in the photographic industry.
Optically enhance the desired wavelength range using known dyes.
I can feel it. The sensitizing dyes may be used alone, but two or more kinds
You may use in combination. With sensitizing dye
A dye that does not have a spectral sensitizing effect, or visible light
Is a compound that does not absorb light, and the sensitizing action of the sensitizing dye
A strengthening supersensitizer may be contained in the emulsion. As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dye, complex merocyanine dye, holopolar
-Cyanine dye, hemicyanine dye, steryl dye and
And hemioxanol dyes are used. Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye. Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, it prevents fog during photographic processing or reduces photographic performance.
End of chemical ripening during chemical ripening for the purpose of keeping the temperature constant
Time and / or after completion of chemical ripening, the silver halide emulsion is
By the time it is applied, the antifoggant or safety agent in the photographic industry
Compounds known as excipients can be added. With a binder (or protective colloid) for silver halide emulsions
For this reason, it is advantageous to use gelatin.
Derivatives, graft polymers of seratin and other polymers,
Other proteins, sugar derivatives, cellulose derivatives, single
Hydrophilicity of synthetic hydrophilic polymer such as ruby or copolymer
Colloids can also be used. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
The layer and other hydrophilic colloid layers are binders (or protective layers).
A hardener that crosslinks molecules to increase film strength.
Can be hardened by using one or more
It Hardener does not need to be added to the processing solution
Although it is possible to add the photosensitive material in an amount sufficient to harden the film,
It is also possible to add a hardening agent to the processing liquid. For example, aldehydes (formaldehyde, glyoxa
, N-methylol, etc.)
Compound (dimethylol urea, methylol dimethyl hydanto
In, etc.), dioxane derivative (2,3-dihydroxy)
Dioxane), active vinyl compounds (1,3,5-tria
Cryloyl-hexahydro-s-triazine, 1,3-
Vinylsulfonyl-2-propanol, etc.), active halo
Gen compound (2,4-dichloro-6-hydroxy-s-
Triazine, etc.), mucohalogenates (mucochloric acid,
Such as mucophenoxycyclo acid), etc., alone or in combination
It can be used together. The silver halide emulsion layer and / or other hydrophilic co-layer of the light-sensitive material
A plasticizer can be added to the Lloyd layer to increase flexibility.
It Preferred plasticizers are those described in RD17643, Section XII, A.
It is a compound. Size of photographic emulsion and other hydrophilic colloid layers of light-sensitive materials
For the purpose of improving stability, etc.
It may contain a dispersion (latex) of the synthetic polymer. For example, alkyl (meth) acrylate, alkoxyal
Kill (meth) acrylate, glycidyl (meth) acry
Rate, (meth) acrylamide, vinyl ester (eg
Vinyl acetate), acrylonitrile, olefins, sulfur
Alone or a combination of terene, etc.
Acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hyaluronic acid
Droxyalkyl (meth) acrylate, sulfoalk
Combination of styrene (meth) acrylate and styrene sulfonic acid
A polymer containing sesame as a monomer component can be used. The emulsion layer of the light-sensitive material contains aromatic compounds during color development processing.
Primary amine developers (e.g. p-phenylenediamine induced)
Conductor, aminophenol derivative, etc.)
Dye-forming couplers that perform pulling reactions to form dyes
Used. The dye-forming coupler is used for each emulsion layer
Form a dye that absorbs the light in the light-sensitive spectrum of the emulsion layer.
Is usually selected as follows.
Yellow dye-forming coupler is magenta in the green-sensitive emulsion layer.
The dye-forming coupler is a cyan dye-type coupler in the red-sensitive emulsion layer.
A synthetic coupler is used. However, depending on the purpose
The silver halide color copy can be used in a different way from the above combination.
You may make a true photosensitive material. These dye-forming couplers are called ballast groups in the molecule.
Couplers have non-diffusing groups with 8 or more carbon atoms
Is desirable. These dye-forming couplers also consist of one molecule
4 molecules of silver ions are reduced to form a dye
2 molecules of silver ion are returned even if it is necessary for 4 equivalence
Either of the two equivalences that need only be derived. Pigment form
The color coupler has a color correction effect on the coupler.
Error by coupling with an oxidant of the developer and developing agent.
Image suppressor, development accelerator, bleaching accelerator, developer, halogen
Silver halide solvent, toning agent, hardener, antifoggant, antifoggant,
Photographically like chemical sensitizers, spectral sensitizers, and desensitizers
Compounds that release useful fragments are included. This
Among these, the development inhibitor is released with development, and the image is
DIR couplers are couplers that improve sharpness and image graininess.
Called. Oxidized product of developing agent instead of DIR coupler
At the same time to produce a colorless compound by coupling reaction with
DIR compounds that release development inhibitors may be used. The DIR couplers and DIR compounds used are
When the inhibitor is directly bonded to the position
Is coupled to the coupling position via
Intramolecular nucleophilic reactions within the group that is released by
Bound so that the inhibitor is released by the child transfer reaction etc.
Things (Timing DIR coupler and Timing DIR combination
(Referred to as a thing) is included. In addition, the inhibitor is also diffusible after withdrawal.
Depending on the application, those that are not so diffuse
Can be used alone or in combination. Aromatic first grade
Coupling reaction with the oxidant of amine developer
Colorless couplers that do not form elements (also called competing couplers)
Can also be used in combination with a dye-forming coupler. In the present invention, a coupler represented by the general formula [1]
It does not matter if you use an outside yellow dye-forming coupler together.
Yes. As a yellow dye-forming coupler that can be used in combination,
A known acylacetanilide coupler is preferably used
You can Of these, vivaloylacetani
Lido compounds are advantageous. As a magenta dye-forming coupler, a known 5-pyrazo
Ron coupler, pyrazolobenzimidazole coupler
-, Pyrazolotriazole couplers, open-chain acyl ace
Tonitol coupler, indazolone coupler, etc.
You can Examples of magenta color couplers that can be used
Examples are, for example, U.S. Patent Nos. 2,600,788 and 2,983,608,
No. 3,062,653, No. 3,127,269, No. 3,311,476
Issue No. 3,419,391, No. 3,519,429, No. 3,558,31
No. 9, No. 3,582,322, No. 3,615,506, No. 3,834,9
08, 3,891,445, West German patent 1,810,464, West Germany
Patent application (OLS) 2,408,665, 2,417,945, 2,418,9
No. 59, No. 2,424,467, Japanese Patent Publication No. 40-6031, JP-A No. 49-740
No. 27, No. 49-74028, No. 49-129538, No. 50-60233,
50-159336, 51-20826, 51-26541, 52-42
No. 121, No. 52-58922, No. 53-55122, Japanese Patent Application No. 55-110943
And the like. Cyan dye-forming couplers include phenol or
Futor couplers are commonly used. You can use
Specific examples of uncoloring couplers include, for example, U.S. Pat.
No. 0, No. 2,474,293, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,326, No. 3,758,
No. 308, No. 3,893,044, JP-A-47-37425,
50-10135, 50-25228, 50-112038, 50-1174
No. 22, No. 50-130441, etc.,
The coupler described in JP-A-58-98731 is preferred.
Good Dye formation without the need for adsorption on the silver halide crystal surface
Coupler, colored coupler, DIR coupler, DIR combination
Objects, image stabilizers, antifoggants, UV absorbers, fluorescent
Among the whitening agents, hydrophobic compounds are solid dispersion method, LATEC
Dispersion method, oil-in-water emulsion dispersion method, etc.
This is the chemical structure of hydrophobic compounds such as couplers.
It can be selected as appropriate according to the structure or the like. Oil-in-water type
The emulsion dispersion method disperses hydrophobic additives such as couplers.
A conventionally known method can be applied, and a boiling point of about 150 ° C or higher is usually used.
Low boiling point and / or water-soluble as needed for high boiling point organic solvent
Dissolves in combination with an organic solvent, giving hydrophilicity such as gelatin aqueous solution.
Stirrer and homogenizer using a surfactant in a hydrophilic binder
Iser, colloid mill, flowgit mixer, ultrasonic
After emulsifying and dispersing with a dispersing device such as a device,
It may be added to the hydrophilic colloid solution. Dispersion or min
You may add a step to remove low boiling point organic solvent at the same time
Yes. As a high boiling point solvent, a solvent that does not react with the oxidant of the developing agent.
Nole derivative, phthalic acid alkyl ester, phosphoric acid
Steal, citrate, benzoate, alk
Lamide, 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 instead of high-boiling solvents
Organic solvents can be used. It has a low boiling point and is practically insoluble in water.
Ethyl acetate, propyl acetate as machine solvent
Butyl acetate, butanol, chloroform, four
Carbon chloride, nitromethane, nitroethane, benzene, etc.
is there. Dye forming coupler, DIR coupler, Colored coupler, D
IR compounds, image stabilizers, anti-foggants, UV absorption
Agent, optical brightener etc. are carboxylic acid, sulfonic acid etc.
When it has an acid group, it is hydrophilic as an alkaline aqueous solution.
It can also be incorporated into a colloid. Hydrophobic compounds may be used alone or in combination with high boiling solvents.
Dissolved in different solvents and dispersed in water using mechanical or ultrasonic waves
As an auxiliary agent for dispersion, an anionic surfactant,
Nonionic surfactant, cationic surfactant and amphoteric field
A surface active agent can be used. Emulsion layers of light-sensitive material (same color-sensitive layer and / or different layers)
The oxidant of the developing agent or the electron transfer agent is transferred between the color-sensitive layers.
Movement to cause color turbidity, deterioration of sharpness, graininess
Use a color antifoggant to prevent the
You can The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer is provided between adjacent emulsion layers and contained in the intermediate layer.
Good. An image stabilizer to prevent deterioration of dye images
Can be used. Compounds that can be preferably used
The product is as described in RD17643, item VII J. Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials
Turnip caused by discharge caused by material being charged due to friction, etc.
To prevent deterioration and deterioration of the image due to ultraviolet rays.
An external line absorbent may be included. Magenta dye formation by formalin during storage of light-sensitive materials
To prevent the deterioration of couplers etc.
A phosphorus scavenger can be used. Dye, UV absorber, etc. are added to the hydrophilic colloid layer of the photosensitive material.
When included, they are a medium such as a cationic polymer.
It may be mordanted with a dyeing agent. Silver halide emulsion layer of photosensitive material and / or other hydrophilic
Change the developability of development accelerator, development retarder, etc.
A compound to be compounded and a bleaching accelerator can be added. Development accelerator
The compound which can be preferably used as is RD17643
A compound described in the paragraphs X to B of the section XXI, which is a development retarder.
Is a compound described in Item XXI, Item E of 17643. Development promotion
Black-and-white developing agent and / or its
A curser may be used. The emulsion layer of the photographic light-sensitive material has increased sensitivity and contrast.
Polyalkylene oxide or
Derivatives of ethers, esters, amines, etc.
Terpo compounds, thiomorpholines, quaternary ammonium
Compound, urethane derivative, urea derivative, imidazole derivative
It may include a conductor or the like. The photosensitive material includes a filter layer, an antihalation layer, and
Auxiliary layers such as anti-radiation layer can be provided
It In these layers and / or emulsion layers, during development processing
Contains dyes that may bleach or bleach from light-sensitive materials
You may be allowed to. Such dyes include oxonol
Dye, hemioxonol dye, styryl dye, merocyan
Examples include nin dyes, cyanine dyes, azo dyes, etc.
Wear. Silver halide emulsion layer of photosensitive material and / or other hydrophilic
Of light-sensitive material on the photosensitive colloid layer, improvement of writing property,
A matting agent is used to prevent sticking of the photosensitive materials to each other.
Can be added. Any matting agent can be used
However, for example, silicon dioxide, titanium dioxide,
Gnesium, aluminum dioxide, barium sulfate, carbonic acid
Polymers of calcium, acrylic acid and metacrylic acid and
Such as ester, polyvinyl resin, polycarbonate
Rabini includes styrene polymers and their copolymers.
To be The matting agent preferably has a particle size of 0.05 μ to 10 μ.
Yes. The amount to add is 1 to 300 ng / m²Is preferred. Lubricants may be added to the photosensitive material to reduce sliding friction.
Wear. You can add an antistatic agent to the photosensitive material for the purpose of antistatic.
Wear. The antistatic agent is a belt on the side of the support where the emulsion is not laminated.
It may be used in the antistatic layer, and it may be used in combination with the emulsion layer and / or the support.
The protective rollers other than the emulsion layer on the side where the emulsion layers are stacked
It may be used for the id layer. Antistatic used preferably
The stopping agent is a compound described in RD17643 XIII. Photographic emulsion layer and / or other hydrophilic colloid layer of light-sensitive material
Includes coating property improvement, antistatic property, slip property improvement, emulsion dispersion,
Prevents adhesion and improves photographic properties (development acceleration, film hardening, sensitization, etc.)
Various surfactants can be used for the purpose of
It The support used in the light-sensitive material of the present invention includes cellulose acetate.
Source, cellulose nitrate, polystyrene, polyvinyl chloride
, Polyethylene terephthalate, polycarbonate,
Film made of semi-synthetic or synthetic polymer such as polyamide
Is preferred. The photosensitive material may be corona discharge or ultraviolet
Directly or on the surface of the support after irradiation with rays, flame treatment, etc.
Adhesiveness, antistatic property, dimensional stability, wear resistance, hardness,
Antihalation properties, friction properties, and / or other characteristics
Applied through one or more subbing layers to improve
May be. When coating photosensitive material, increase viscosity to improve coatability
Agents may be used. Also, for example, like hardeners,
Because it is fast, if it is added to the coating solution beforehand, it will gel before coating.
For things that cause aging, static mixer
It is preferable to mix them just before coating by using, for example. As a coating method, it is possible to coat two or more layers at the same time.
Extrusion coating and curtain
Is especially useful, but depending on the purpose,
Coating is also used. Also, the coating speed can be selected arbitrarily.
it can. The surfactant is not particularly limited, but for example saponi
Natural surfactants such as amines, alkylene oxides, glycerides
Nonionic surfactants such as phosphorus and glycidol, high
Alkylamines, quaternary ammonium salts, viridi
And other heterocycles, phosphonium or sulfonium
Cationic surfactants such as carboxylic acids, sulfonic acids,
Contains acidic groups such as phosphoric acid, nitrates, and phosphates
Anionic surfactant, amino acids, aminosulfonic acid
, Sulfuric acid or phosphoric acid esters of amino alcohol, etc.
You may add the amphoteric surfactant of. Also similar purpose
For this reason, it is possible to use a fluorochemical surfactant.
It To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing is a color development processing
Process, bleaching process, fixing process, washing process
If necessary, perform a stabilization process, but use a bleaching solution.
1-bath bleaching instead of physical processing and processing using fixer
A bleach-fixing process can also be performed using a fixer.
However, color development, bleaching and fixing can be done in one bath.
Perform monobath processing process using bath development bleach-fixing solution
You can also do things. In combination with these treatment steps, the pre-dural treatment step,
Performs neutralization process, stop-fixing process, post-hardening process, etc.
May be. Instead of the color development process in these processes
Color developing agent or its breaker in the material
Activator solution is included in the development process.
You may carry out the process of the tibator, or its monobath treatment
Activator treatment can be applied to. these
A typical process is shown below during the process. (These processes
As the final process, washing process, washing process and stability
One of the chemical treatment steps is performed. ) ・ Color development processing step-bleaching processing step-fixing processing step-Color development processing step-bleach fixing processing step-Pre-hardening processing step-color development processing step-stop fixing processing step
Process-washing process-bleaching process-fixing process-washing
Processing step-Post-hardening processing step-Color development processing step-Water washing processing step-Supplementary color development processing
Process-Stopping process-Bleaching process-Fixing process-Activator process-Bleaching process-Activator process-Bleaching process-Fixing process
・ Monobath treatment process The treatment temperature is usually selected in the range of 10 ℃ to 65 ℃, but 65 ℃
The temperature may be higher than that. Preferably at 25 ℃ ~ 45 ℃
Be treated. Color developing solutions are generally alkaline water containing a color developing agent.
It consists of a solution. Color developing agent is aromatic primary amine color
A developing agent, aminophenol-based and p-phenylene
Zinamine derivatives are included. These color developing agents
Can be used as salts of organic and inorganic acids, for example
For example, salt machine acid, sulfate, p-toluenesulfonate, sulfite
Use salt, oxalate, benzene sulfonate, etc.
You can These compounds generally account for about 0.1 for Color Developer 1.
~ 30g concentration, more preferably about color developer 1
Used at a concentration of about 1 to 15 g. Less than 0.1g
Sufficient color density cannot be obtained with the added amount. Examples of the aminophenol-based developer include o-a
Minophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-tolu
Ene, 2-oxy-3-amino-1,4-dimethyl-be
And the like are included. Particularly useful primary aromatic amine color developing agents are N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl group and phenyl group may be substituted or not
May not be replaced. Among them, especially useful
As an example of compound, N-N-dimethyl-p-phenylenedia
Min hydrochloride, N-methyl-p-phenylenediamine hydrochloride
Salt, N, N-dimethyl-p-phenylenediamine hydrochloric acid
Salt, 2-amino-5- (N-ethyl-N-dodecylami)
No) -toluene, N-ethyl-N-β-methanesulfone
Amidoethyl-3-methyl-4-aminoaniline sulfate
Salt, N-ethyl-N-β-hydroxyethylaminoani
Phosphorus, 4-amino-3-methyl-N, N-diethylani
Phosphorus, 4-amino-N- (2-methoxyethyl) -N-
Ethyl-3-methylaniline-p-toluenesulfone
And the like. The above color developing agents may be used alone or in combination of two or more kinds.
You may use it. Furthermore, the color developing agents are color
It may be incorporated in the photographic material. In this case, halogenation
Use silver color photographic light-sensitive material with alkali instead of color developer.
It is also possible to treat with a solution (activator solution),
Immediately after the alkaline solution treatment, a bleach-fixing treatment is carried out. The color developing solution used in the present invention is usually used as a developing solution.
Alkaline agents such as sodium hydroxide, potassium hydroxide
Aluminum, ammonium hydroxide, sodium carbonate, potassium carbonate
, Sodium sulfate, sodium metaborate or borax
Etc., and various additives such as benzyl.
Alcohol, alkali metal halides such as bromine carbonate
As a development regulator, such as lithium or potassium chloride
As a preservative, for example, citrazinic acid, etc.
It may contain min or sulfite. Further various erase
Foams and surfactants, methanol, dimethylform
Use an organic solvent such as amide or dimethyl sulfoxide.
It can be included for convenience. The pH of the color developer used in the present invention is usually 7 or higher,
It is preferably about 9 to 13. In addition, the color developing solution used in the present invention may be used, if necessary.
Diethylhydroxyamine, tetron as antioxidant
Acid, tetronamide, 2-anilino ethanol, dihydride
Roxyacetone, secondary aromatic alcohol, hydroxam
Acid, bentose or hexose, pyrogallol-1,
It may contain 3-dimethyl ether or the like. The color developer used in the present invention contains a sequestering agent
Then, various chelating agents can be used in combination. example
For example, as the chelating agent, ethylenediaminetetraacetic acid, die
Amine polycarboxylic acids such as thylenetriaminopentaacetic acid, 1
-Hydroxyethylidene-1,1'-diphosphonic acid, etc.
Organic phosphonic acid, aminotri (methylenephosphonic acid)
Aminopolyphos such as ethylenediaminetetraphosphoric acid
Oxicals such as sulfonic acid, citric acid or gluconic acid
Boronic acid, 2-phosphonobutane-1,2,4-tricarbo
Phosphonocarboxylic acid such as acid, triboriphosphoric acid or
Polyhydroxylation of polyphosphoric acid such as hexametaphosphoric acid
Examples include compound. As mentioned above, the bleaching process is the same as the fixing process.
It may be performed or may be performed individually. As a bleach
Is a metal complex salt of an organic acid such as polycarboxylic acid.
Organics such as acids, aminopolycarboic acids or acids, citric acid
Acid that is coordinated with metal ions such as iron, cobalt, and copper
Is used. Most preferred organic of the above organic acids
As the acid, polycarboxylic acid or aminopolycarboxylic acid
Is mentioned. Specific examples of these include ethylene diami
Tetraacetic acid, diethylenetriaminepentaacetic acid, ethyl
Diamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nit
Lilotriacetic acid, cyclohexanediaminetetraacetic acid, a
Minodiacetic acid, dihydroxyethylglycine citric acid (or
Tartaric acid), ethyl ether diamine tetraacetic acid, glyco
Ether diamine tetraacetic acid, ethylene diamine
Trapropionic acid, phenylenediamine tetraacetic acid, etc.
Can be mentioned. These polycarboxylic acids are
Limetal salt, ammonium salt or water-soluble amine salt
You may. These bleaches are 5-450g /, better
Use at 20-250g /. In addition to the bleaching agents described above, the bleaching solution should be preserved as necessary.
A liquid having a composition containing sulfite as an agent is applied. or,
Contains ethylenediaminetetraacetate iron (III) complex salt bleach
A large amount of halide such as ammonium bromide
A bleaching solution having the above composition may be used. The halogen
Compounds include ammonium bromide, hydrochloric acid, and odor.
Hydrofluoric acid, lithium bromide, sodium bromide, potassium bromide
Aluminum, sodium iodide, potassium iodide, ammonium iodide
Etc. can also be used. The bleaching solution used in the present invention is described in JP-A-46-280,
45-8506, 46-556, Belgian Patent No. 770,910,
JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and
Various bleaching accelerators described in No. 49-42349 are added.
Can be added. The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
5 used, preferably 4.5-8.0, most preferred
It is preferably 5.0 to 7.0. It is recommended to use a fixer having a commonly used composition.
it can. As a fixing agent, it can be used for normal fixing process.
A compound that reacts with silver halide to form a water-soluble complex salt
Compounds such as potassium thiosulfate, sodium thiosulfate
Thiosulfate such as ammonium thiosulfate, thiocyanate
Potassium acid salt, sodium thiocyanate, thiocyanic acid
Thiocyanates such as ammonium, thiourea, thioe
Ether is a typical example. These fixatives
5g / or more, use in an amount that can be dissolved, but generally
Is used at 70-250g /. In addition, a part of the fixing agent
It can be contained in the white tank, and on the contrary, a part of the bleaching agent can be determined.
It can also be contained in the bath. The bleaching solution and / or the fixing solution are borax and sodium hydroxide.
, Potassium hydroxide, sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
Various pH buffers such as ammonium and ammonium hydroxide
Rui can be contained in combination of two or more
It Furthermore, various optical brighteners, antifoaming agents or interfaces
An activator can also be included. Also, hydroxyl
Bisulfite addition of amine, hydrazine and aldehyde compounds
Preservatives for substances, organic chelates such as aminopolycarboxylic acids
Agents or stabilizers such as nitro alcohol and nitrates, water
Hardeners such as soluble aluminum salts, methanol, dimethy
Organic solvents such as rusulfomido and dimethylsulfoxide
Can be appropriately contained. The fixer is used at a pH of 3.0 or above, but generally 4.5-10
Used in, preferably used in 5-9.5, most preferred
It is 6-9. The bleaching agent used in the bleach-fixing solution is the bleaching agent
The metal complex salts of organic acids described above can be mentioned as
The compound and the temperature of the processing solution should be the same as the above bleaching process.
It is the same as in. In addition to the bleaching agent as described above, the emulsion layer fixing solution contains silver halide.
Contains a fixing agent and, if necessary, sulfite as a preservative
A liquid having the composition contained is applied. Also, ethylene diami
Iron (III) tetraacetate complex salt bleach and the silver halide fixing described above
Add a small amount of other halide such as ammonium bromide
A bleach-fix solution consisting of the added composition, or vice versa
It does not consist of a composition in which a large amount of halide such as monium is added.
Bleach-fixing solution and iron diamine tetraacetate (II
I) Complex salt bleach and a large amount of halogen such as ammonium bromide
Special bleach-fixing solution with a composition consisting of a combination of
Can also be used. As the halide, bromide
Hydrochloric acid, hydrobromic acid, and lithium bromide in addition to ammonium
Um, sodium bromide, potassium bromide, sodium iodide
Also use aluminum, potassium iodide, ammonium iodide, etc.
You can Silver halide fixing that can be included in bleach-fixing solutions
Examples of the fixing agent include the fixing agents described in the fixing processing step.
You can Fixer concentration and bleach-fix solution
For the pH buffer and other additives that can
The same as in the processing step. The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5,
It is also preferably 6.5 to 8.5. [Example-1] Specific examples of the present invention will be described below.
The embodiment of is not limited to these. In all the examples below, silver halide photographic light-sensitive materials
Unless otherwise specified, the addition amount in the ingredients is 1 m.^TwoHit one
Show. Converting silver halide and colloidal silver to silver
Indicated. On a triacetyl cellulose film support, shown below.
Each layer of such composition is sequentially formed from the support side,
A color photographic element sample 1 was prepared. Sample-1 (Comparative) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver. Second layer; intermediate layer (I.L.) 2,5-di-t-octylhydroquinone emulsified dispersion
A gelatin layer containing. Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RH-1) average grain size () 0.30 μm, from AgBrI containing 6 mol% AgI
Monodisperse emulsion (Emulsion I) ... Silver coating amount 1.8g / m² Sensitizing dye I: 6 × 10 for 1 mol of silver^-FiveMolar sensitizing dye II: 1.0 x 10 per mol of silver^-FiveMolar Cyan coupler (C-1) ………… 0.06 mol to 1 mol of silver Colored cyan coupler (CC-1) ……… 0.003 mol to 1 mol of silver DIR compound (D-1) ……… 1 silver 0.0015 moles to moles DIR compound (D-2) ..... 0.002 moles to 1 mole of silver 4th layer; high-sensitivity red-sensitive silver halide emulsion layer (RH-1) average grain size () 0.5 μm, From AgBrI containing 7.0 mol% AgI
Monodisperse emulsion (Emulsion II): Silver coating amount 1.3g / m² Sensitizing dye I: 3 × 10 for 1 mol of silver^-FiveMolar sensitizing dye II: 1.0 × for 1 mol of silver_10-5Molar cyan coupler (C-1) ………… 0.02 mol per 1 mol silver Colored cyan coupler (CC-1) ……… 0.0015 mol per mol silver DIR compound (D-2) ……… 1 silver 0.001 mol per mol Fifth layer; Intermediate layer (IL) Gelatin layer, same as second layer. 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-1 ..... Coating silver amount 1.5g / m² Sensitizing dye III: 2.5 × 10 for 1 mol of silver^-FiveMolar sensitizing dye IV: 1.2 × 10 per mol of silver^-FiveMol Magenta coupler (M-1) ………… 0.050 mol per 1 mol silver Colored magenta coupler (CM-1) ……… 0.009 mol per mol silver DIR compound (D-1) ……… 1 silver 0.0010 moles to moles DIR compound (D-3) ………… 0.0030 moles to 1 mole of silver 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) emulsion-II ………… coated silver Quantity 1.4g / m² Sensitizing dye III: 1.5 × 10 for 1 mol of silver^-FiveMolar sensitizing dye IV: 1.0 × 10 for 1 mol of silver^-FiveMole Magenta coupler (M-1) ………… 0.020 mol per 1 mol silver Colored magenta coupler (CM-1) ……… 0.002 mol per mol silver DIR compound (D-3) ……… 1 silver 0.0010 mol per mol 8th layer; yellow filter layer (YC-1) Yellow colloidal silver and 2,5-di-t-octylhydroxy
A gelatin layer containing a non-emulsion dispersion. Layer 9: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion layer (Emulsion III) consisting of AgBrI with an average grain size of 0.48 μm and 6 moles of AgI ... Silver coating amount 0.9 g / m² Sensitizing dye V ........ 1.3 × 10 for 1 mol of silver^-FiveMol Yellow coupler (A-1): 0.34 mol for 1 mol of silver 10th layer; High-sensitivity blue-sensitive emulsion layer (BH-1) Monodispersed AgBrI with average grain size 0.8 μm and AgI 15 mol% Emulsion (Emulsion IV): Silver coating amount 0.5g / m² Sensitizing dye V: 1.0 × 10 for 1 mol of silver^-FiveMol Yellow coupler (A-1) ………… 0.13 mol to 1 mol silver DIR compound (D-2) ………… 0.0015 mol to 1 mol silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide (AgI 1 mol% average particle size 0.07 μm) Silver coating amount 0.5 g /
m² Gelatin layer containing UV absorbers UV-1 and UV-2. 12th layer; 2nd protective layer (Pro-2) Polymethylmethacrylate particles (diameter 1.5 μm) and foil
Gelatin layer containing lumarin scavenger (HS-1) In addition to the above composition, a gelatin hardener (H-1) and
Surfactant was added. Next, as shown in Table 1, the second, third, and fourth samples-1
The layer is provided with a compound that forms an unsharp positive image of the present invention.
Each of them was added, while the 9th and 10th layers developed the yellow color of the present invention.
Samples 2 to 10 to which couplers were added were prepared. The compounds contained in each layer of Sample 1 are as follows. Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl
Le-3,3'-di- (3-sulfopropyl) thiacarbo
Cyanine hydroxide sensitizing dye II; anhydro 9-ethyl-3,3'-di-
(3-Sulfopropyl) -4,5,4 ', 5'-diben
Zothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-
Ethyl-3,3'-di- (3-sulfopropyl) oxa
Carbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3,3'-di-
(3-Sulfopropyl) -5,6,5 ', 6'-diben
Zooxacarbocyanine hydroxide sensitizing dye V; anhydro 3,3'-di- (3-sulfop
Ropil) -4,5-benzo-5'-methoxythiacani
The Each sample No. 1 to 10 created in this way is
After exposure using the above, the following development processing was performed. Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in each processing step is as follows. On the street
is there. [Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydrde
Roxyethyl) -aniline / sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxyamine / 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid / trisodium salt (monohydrate) 2.5 g Potassium hydroxide Add 1.0g water to make 1. [Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to adjust pH to 6.0 with ammonia water.
adjust. [Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 1 and adjust pH = 6.0 with acetic acid.
It [Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1. For each of the obtained samples, the relative sensitivity (S),
Gradation (γ) and sharpness (MTF) were measured. as a result
Is shown in Table 2. The relative sensitivity (S) is the exposure that gives a fog density +0.3.
It is the relative value of the reciprocal of the quantity, and the sensitivity of sample No. 1 is 100.
Shown by value. Gradation (γ) is the exposure of 10 which gives fog density +0.3.
If the density at the double exposure dose point (ΔlogE = 1.0) is D, γ
= {D- (fog + 0.3)} / 1.0. The effect of improving sharpness is the MTF (Modulation Transfe
r Function), MTF at 10 lines / mm and 50 lines / mm
Is shown as relative value (sample No. 1 is 100). As is clear from Table 2, the present invention is compared with Sample 1.
Compound used alone to form unsharp positive images
When it is done (Samples 2, 3 and 4), there is an effect of improving the sharpness.
However, the sensitivity is lowered and the tone becomes softer. On the other hand, the yellow emission of the present invention
High frequency side when using color coupler alone (Sample 5)
Although there is some improvement in the sharpness of (50 lines / mm MTF), it is low
Improvement on the frequency side (10 lines / mm MTF) is small,
The degree and gradation are also improved compared to Comparative Sample 1.
Unable to find such a contribution. However, the samples 6 to 10 according to the combination of the present invention have low frequencies.
・ Improved MTF and sharpness at both high frequencies
I understand. Furthermore, in these samples (6-10),
It can be seen that desensitization and softening are extremely small. That is, this fruit
According to the first embodiment, the object of the present invention is achieved by the configuration of the present invention.
You can see that it is done. [Example 2] In the sample 1 of Example-1, the present invention was applied to the fifth, sixth and sixth layers.
Compounds that form a bright unsharp positive image are
The yellow color forming coupler of the present invention was added to each of 10 layers.
Samples 11 to 19 were prepared with the contents shown in Table 3. The obtained samples 11 to 19 and the sample 1 of Example-1 were carried out.
The same processing as in Example-1 was performed, and the results shown in Table 4 were obtained.
Got As can be seen from Table 4, the sharpness is improved by the constitution of the present invention.
Of the present invention, which is excellent in sensitivity and improves sensitivity and gradation.
You can see that the goal has been achieved.

Claims (1)

[Claims] 1. At least one light-sensitive silver halide emulsion layer on a support contains a yellow coupler represented by the following general formula, and a layer containing the coupler and / or a color sensitivity different from that. A negative-type silver halide photographic light-sensitive material comprising a means for forming an unsharp positive image in combination with a silver halide emulsion layer having General formula [1] In the formula, R ¹ , R ² and R ³ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, a sulfonamide group, Represents a sulfamoyl group. R ⁴ , R ⁵ , R ⁶ and R ⁷ may be the same or different,
Each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, or a sulfonamide group. W represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a dialkylamino group. X represents a hydrogen atom or a removable group.