JP3485661B2 - Surface latent image type silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface latent image type halogenation.
It relates to a silver photographic light-sensitive material. In particular, the present invention
Surface latent image type silver halide photography with high contrast and sharp feet
Light materials. [0002] 2. Description of the Related Art Basic performance of silver halide photographic materials and
High sensitivity, fine graininess and low fog
Is being used. One of the means to satisfy them is metal dough
Technology. Metal doping technology is used for silver halide grains.
Modifies physical properties and converts photoelectrons into a latent image with development activity
It is performed for the purpose of increasing the rate (quantum sensitivity).
Specifically, metal doping technology refers to metal ion alone or distribution.
Incorporates metal complexes containing ligands into silver halide grains
This is a doping technique. By metal doping,
The properties of the silver logenide grains have been modified to improve overall emulsion performance.
Can be improved to wait. General and practical
Surface latent image type silver halide photographic emulsions
Is desired. Sensitive materials especially for graphic arts
Therefore, it is desired that the contrast is high even if the sensitivity is reduced.
You. This contrast is represented by the exposure amount on the horizontal axis and the optical density on the vertical axis.
That the slope of the gradation part (linear part) of the
means. Regarding the gradation, the foot of the characteristic curve (optical density
Area where the exposure starts to rise)
It is also important that the bite is steep). Similarly, color marking
Even with silver halide photographic materials such as paper, the characteristic curve
That the part corresponding to the low density part of the
The sharpness of the image is clear
Desirable to get. [0003] Research Disclosure (Reser)
ch Disclosure), 17643, section IA
Can be introduced during grain formation for metal doping technology
A metal ion or metal complex is described. Metal dope
Typical examples of metal complexes used early in the technology
Is shown in U.S. Pat. No. 2,448,060,
Platinum, palladium, iridium, rhodium and rutheni
Metal complex. These water-soluble metal complexes
Function as a fog prevention and stabilizer
You. In particular, hexacoordinate metal complexes of palladium (IV valence) have increased.
Also shows sensation. The complex described in this document is chloride
Or halides such as bromides as ligands
Have. U.S. Pat. No. 3,690,888 discloses polyvalent metals
Discloses a method for producing silver halide containing ions.
You. Its manufacturing method is mainly based on acrylic polymer.
Silver halide grains in the presence of protective colloid
The step of performing The polyvalent metal ion used is
Sumus, iridium, lead or osmium ions
Have been In addition to metal ions,
Complexes are halogens such as chloride or bromide
A compound as a ligand. The above literature is based on metal ions
Is obtained by incorporation into silver halide grains.
Disclose the effect. With respect to dopants containing cyanide ions
Japanese Patent Publication No. 48-35373 discloses a cyanide ion
Hexacyano metal complex of iron
Disclosed are yellow blood salts and red blood salts. The effect of this invention is
The complex contains iron ions, regardless of the type of ligand
Limited to cases. U.S. Pat. No. 3,790,390 discloses that
Contains cyano complexes of iron (II), iron (III) and cobalt (III)
And disclosed silver halide emulsions containing spectral sensitizing dyes.
You. U.S. Pat. No. 4,847,191 describes 3, 4, 5, or
Or rhodium (III) complexes with six cyano ligands
Disclosed are silver halide grains formed in the presence. This sentence
We have high expectations for silver halide emulsions containing these grains.
Reports a reduction in illuminance failure. The above literature also shows that
On is incorporated into silver halide grains.
The result is disclosed. JP-A-2-20853 and JP-A-2-20
No. 854, each discloses a Leni having four or more cyano ligands.
Of ruthenium, ruthenium, osmium or iridium complexes
Disclosed are silver halide grains formed in the presence. these
Describes that sensitivity of emulsions containing these grains
And time stability of gradation and improvement of low light failure
Describe good. JP-A-2-20852 and JP-A-2-208
Nos. 55, 3-118535 and 3-11853
No. 6 each discloses a cyanide ion and a bridging ligand (eg, N
O, NS, CO, (O)_Two)). This
In these references, a hexagonal structure consisting of a metal ion and six ligands is described.
Coordination metal complex has one silver ion and six neighbors inside the crystal
Substituting 7 vacancies for halide ions
A new concept of being doped by
You. JP-A-6-51423 (European Patent No. 0
No. 573066A1) discloses an internal latent image type direct positive
Invention of doping hexacyano metal complex in silver halide emulsion
Is disclosed. The metals in the complex include chromium and man
Cancer, cobalt, iridium, ruthenium, rhodium,
Rhenium and osmium are described. The invention
The effect of the internal latent image type
The objective is to obtain a positive silver halide emulsion. Internal latent image type
Direct positive silver halide emulsions are mainly used in image exposure.
Silver halide emulsion forming latent image inside silver halide
It is. Using the special properties of this emulsion,
An image can be formed. In specific image formation,
After forming an internal latent image by image exposure, the surface developer (internal latent image
Not selectively developing silver halide grains having
Liquid) for uniform exposure or nucleating agent treatment
Is carried out. Due to these complicated processes, the internal latent image type
The positive contact silver halide emulsion is relatively (the following surface latent image type
Low sensitivity (compared to silver halide emulsions). For this reason,
Improvement of internal latent image type direct positive silver halide emulsion
Is always required to have high sensitivity. On the other hand, ordinary silver halide emulsions
Is a surface latent image type, and is mainly used for image exposure.
A latent image is formed on the surface of the silver logenide. Surface latent image type halogen
In image formation using a silver halide emulsion, surface exposure is performed by image exposure.
After forming an image, a halogen having a surface latent image using a developing solution
The silver halide particles are selectively developed. Surface latent image type silver halide
Emulsions are relatively sensitive. For this reason, depending on the application
Improves other properties at reduced sensitivity (e.g.,
There is a case where it is desired to make the gradation high. This
The effect of high contrast accompanied by a decrease in sensitivity (desensitized high contrast) is described above.
As in the effect of the invention described in Japanese Unexamined Patent Publication No. 6-51423,
It is distinguished from a high contrast effect without a decrease in sensitivity. As described above, the internal latent image type emulsion and the surface latent image
In the type emulsion, the mechanism of image formation is fundamentally different. this
Therefore, the effect of the metal doping is also different from that of the internal latent image type emulsion.
The surface latent image type emulsion may be significantly different. Mentioned earlier
As described above, the metal doping technology converts photoelectrons into a latent image
The purpose is to change the efficiency (quantum sensitivity)
Is implemented. As a result, the target latent image is
Depending on whether it is present or on the particle surface
The effect of the genus dope varies greatly. [0009] SUMMARY OF THE INVENTION An object of the present invention is to provide desensitization.
Surface latent image type halogen with high contrast and good characteristic curve
An object of the present invention is to provide a silver halide photosensitive material. [0010] According to the present invention, there is provided a method for reducing the number of substrates on a support.
Has at least one surface latent image type silver halide emulsion layer
A surface latent image type silver halide photographic material,
The latent image type silver halide grains of the agent layer are represented by the following formula (I):
Characterized by containing a cyanochrome complex ion represented
Provided is a surface latent image type silver halide photographic material. (I) [Cr (CN)_6-n L_n ]^m- Where L is H_Two O or OH, n is 0 or 1
And m is 3 or 4. Surface latent image type silver halide photographic light-sensitive material of the present invention
The material may be implemented in the following modes (2) to (11).
it can. (2) The surface latent image type silver halide grains are
Chromium complex ion is added in an amount of 1 × 10^-8
~ 1 × 10^-2The surface latency according to (1), which is contained in a molar range.
Image-type silver halide photographic material. (3) The surface latent image type silver halide particles contain silver chloride.
Having a halogen composition such that the ratio is 50 mol% or more
The surface latent image type silver halide photographic material according to (1). (4) The surface latent image type silver halide grains contain silver chloride.
Has a halogen composition such that the ratio is 80 mol% or more.
The surface latent image type silver halide photographic material according to (3). (5) The above surface latent image type silver halide emulsion layer
Described in (1) further containing a mercaptoheterocyclic compound.
Surface latent image type silver halide photographic material. (6) The surface latent image type silver halide emulsion layer further comprises
The lecaptoheterocyclic compound is used in an amount of 1 mole per mole of silver halide.
× 10^-Five~ 5 × 10^-2Described in (5), including in the molar range
Surface latent image type silver halide photographic material. (7) The surface latent image type silver halide emulsion layer further comprises
The surface latent image according to (1), which contains a triazaindene compound
Type silver halide photographic material. (8) The surface latent image type silver halide emulsion layer further comprises
The traazaindene compound is added in an amount of 1 per mole of silver halide.
× 10^-Five~ 3 × 10^-1Described in (7) including in the molar range
Surface latent image type silver halide photographic material. (9) The above surface latent image type silver halide grains
But also iron, ruthenium, osmium, cobalt, b
(1) Including complex ions of indium or iridium
Surface latent image type silver halide photographic material. (10) having a coating pH value in the range of 4.0 to 6.5
The surface latent image type silver halide photographic material according to (1). (11) having a coating pH value in the range of 5.0 to 6.5
The surface latent image type silver halide photographic material according to (10).
Fees. [0014] According to the present inventors' research, the cyanochrome complex
When ions are doped into surface latent image type silver halide grains,
Although the sensitivity is significantly reduced, it is possible to obtain a very hard image.
It turned out. In particular, the sharpness of the characteristic curve
Be improved. As mentioned earlier, general and practical surfaces
Latent image type silver halide photographic emulsions
Tone may be desired. In particular, photographic paper and paper
In light-sensitive materials for graphic arts, gradation is more important than sensitivity.
Image quality is given priority. Surface latent image type silver halide of the present invention
Photosensitive materials are very advantageous for such applications where image quality is prioritized.
Can be applied. [0015] DETAILED DESCRIPTION OF THE INVENTION The silver halide light-sensitive material of the present invention
The silver halide emulsion used is of the surface latent image type. Surface descent
Image-type emulsions are mainly silver halide
This is a silver halide emulsion which forms a latent image on the surface of grains. table
The surface latent image type emulsion can be specifically determined as follows.
You. A fixed amount of silver halide emulsion was coated on a transparent support
Prepare two types of samples. 0.01 to 1
The exposure is given at a fixed time in seconds. One sample
Is developed in the following surface developer at 20 ° C. for 5 minutes.
The remaining samples were prepared at 20 ° C. for 5
Develop for minutes. The maximum density of the surface-developed sample is
When the density is higher than the maximum density of the partially developed sample
It is defined as a latent image type silver halide emulsion. This maximum concentration is
It is measured by a usual photographic density measurement method. [0016] ────────────────────────────────────   Surface developer ────────────────────────────────────   2.5 g of N-methyl-p-aminophenol sulfite   1-alcorbic acid 10g   Potassium metanitrate 35g   1 g of potassium bromide   1 liter with water ──────────────────────────────────── [0017] ────────────────────────────────────   Internal developer ────────────────────────────────────   N-methyl-p-aminophenol sulfite 2g   Sodium nitrite (anhydrous) 90g   Hydroquinone 8g   Sodium carbonate (monohydrate) 52.5g   5 g of potassium bromide   0.5 g of potassium iodide   1 liter with water ──────────────────────────────────── In the present invention, the surface latent image type halo as described above is used.
Silver cyanide particles are doped with cyanochrome complex ions.
The cyanochrome complex ion is represented by the following formula (I). (I) [Cr (CN)_6-n L_n ]^m- Where L is H_Two O or OH, n is 0 or 1
And m is 3 or 4. n is preferably
0. m is preferably 3. The cyanochromium complex ion is ionized in an aqueous solution.
Exists in the form of Therefore, the counter ion of the complex ion
Is not so technically important. As a counter cation
Is easily miscible with water and precipitates silver halide emulsion.
What is necessary is just to select the ion which fits. Counter cation
Examples include alkali metal ions (eg, sodium ions,
Potassium ion, rubidium ion, cesium ion,
Lithium ion), ammonium ion and alkyl
Ammonium ions are included. Alkyl ammonium
The ions are shown in the following formula (II). (II) [R¹ R^Two R^Three R^Four N]⁺ Where R¹ , R^Two , R^Three And R^Four Is the carbon
It is a lower alkyl group having 6 or less atoms. Lower alkyl
Examples of groups include methyl, ethyl, propyl, iso-propyl
And n-butyl. R¹ , R^Two , R^Three And R
^Four Are preferably the same. Preferred alkylan
An example of a monium ion is tetramethylammonium
Mion, tetraethylammonium ion, tetrap
Ropylammonium ion and tetra (n-butyl) a
And ammonium ion. The cyanochrome complex ion may be water or water.
Can be used by dissolving in a mixed solvent with an organic solvent
You. Examples of suitable organic solvents that are miscible with water include alcohol
, Ethers, glycols, ketones, esters
And amides. Of cyanochrome complex ion
The solution is added directly to the reaction solution during silver halide grain formation.
Can be added. It also forms silver halide grains.
In aqueous halide solution or other solution
To form particles. Silver halide grains containing cyanochrome complex ions
When doping, it must be present uniformly inside the particles.
it can. In addition, a high concentration of cyanochrome
Complex ions may be doped. In addition, cyanochrome
Using silver halide fine particles doped with complex ions,
Physically ripen silver logenide grains and add cyanochrome to the grain surface phase.
A complex ion may be introduced. Combining the above methods
And can be implemented. Higher concentration due to particle surface layer
A method of doping a cyano metal complex ion is disclosed in
No. 25245, No. 3-18837 and No. 4-20
It is described in each of JP-A-8936. Cyano metal complex ion
A method using doped silver halide fine particles is described in US Pat.
Nos. 5,252,451 and 5,256,530
There is a description. In the case of the cyanochrome complex ion of the present invention
Can be implemented in a similar manner. In principle, cyanok
The rom complex ion is uniformly present inside the silver halide grains.
Preferably. However, in the early stage of particle formation
Fine crystal nuclei (particle size: about 0.04 to 0.2 μm)
The cyanochrome complex ion at the stage of forming
In some cases, the crystal shape of the particles becomes unstable. others
After the formation of fine crystal nuclei is complete,
It is preferred to add complex ions. This small crystal nucleus
The silver halide grains other than
Preferably, the ONs are uniformly present. The doping amount of the cyanochrome complex ion is
1 × 10^-8~ 1 × 10^-2Mole
Is preferably in the range of 1 × 10^-7~ 1 × 10^-3Molar range
Enclosure is more preferable, 1 × 10^-7~ 1 × 10^-FourMole of
A range is most preferred. Add cyanochrome complex ion
When the hydrogen ion concentration in the reaction solution is pH 3 or more
Is preferred. Doping amount of metal complex in silver halide grains
And doping rate is the central metal of the doped metal complex
(Chromium in the case of the present invention)
it can. As the quantification method, atomic absorption method, ICP method (In
ductively Coupled Plasma Spectrometry: Inductive coupling height
Frequency plasma spectroscopy) or ICPMS (Indus
ctively Coupled Plasma Mass Spectrometry;
Plasma mass spectrometry). Examples of cyanochrome complex ions are given below.
You. (I-1) [Cr (CN)₆ ]^3- (I-2) [Cr (CN)_Five (H_Two O)]^3- (I-3) [Cr (CN)_Five (OH)]^Four- A cyanochromium complex is combined with another cyanometal complex.
For showing different photographic effects, it is estimated as follows
it can. When light is absorbed by silver halide grains, photoelectrons
And holes are generated. The lifetime of this excited photoelectron is
It can be measured using the wave photoconductivity method. For example,
VI such as iron, ruthenium, cobalt and iridium
Emulsion doped with Group II hexacyano metal complex
No. 51423), the lifetime of photoelectrons is extended,
A temporally shallow electron trap is created. As is well known,
When a trap is generated, it is certain that the particles contribute to latent image formation.
Rate is increased, and photographic sensitivity is improved. On the other hand, even with the same cyano metal complex,
In the case of cyanochrome complex, the lifetime of excited electrons is measured in the same manner.
It shows a markedly shorter life. With this, cyanok
Lom complex is considered to have strong electron-capturing ability
You. This causes the photographic sensitivity to decrease and the contrast to increase.
It is estimated that it is. As mentioned above, cyanochrome
The photographic effect of the complex, from the viewpoint of the physical properties of the doped particles,
A clear difference from the effect of the hexacyano metal complex of
You. The surface latent image type silver halide emulsion layer is
It is preferred to include a ptheterocyclic compound. Preferred method
The rucaptoheterocyclic compound is represented by the following formula (III)
You. [0029] Embedded image In the formula, Q represents a 5- or 6-membered heterocyclic ring.
Represents an atomic group necessary for formation, and M is a cation.
An aromatic ring (eg, a benzene ring) is condensed with the heterocyclic ring.
You may. Examples of the heterocyclic ring formed by Q include imidazo
Ring, tetrazole ring, thiazole ring, oxazole
Ring, selenazole ring, benzimidazole ring, naphthoy
Midazole ring, benzothiazole ring, naphthothiazole
Ring, benzoselenazole ring, naphthoselenazole ring and
And benzoxazole rings. Clicks indicated by M
Examples of ON include hydrogen ions, alkali metals (eg, sodium
And potassium ions) and ammonium ions.
I will. Particularly preferred mercaptoheterocyclic compounds are
Formulas (III-1), (III-2), (III-3) and (III-
Represented by 4). [0032] Embedded image Where R¹¹Represents a hydrogen atom, an alkyl group,
Coxy group, aryl group, halogen atom, carboxyl group
Or a salt thereof, a sulfo group or a salt thereof, or an
And Z is -NH-, -O- or -S-.
And M is a cation. [0034] Embedded image Where R¹²Is an aryl group or cycloa
A alkyl group, and M is a cation. Aryl group and
And the cycloalkyl group may have a substituent. Ants
Examples of the hydroxyl group and the cycloalkyl group are further represented by the following formula:
Show. [0036] Embedded image Where R¹³, R¹⁴And R¹⁵Respectively
Alkyl, alkoxy, carboxyl or other
Salts, sulfo groups or salts thereof, hydroxyl groups,
Group, amide group, carbamoyl group or sulfonamide
Represents a group, and n is 0, 1 or 2. R of the formulas (III-1) and (III-2)¹¹, R
¹³, R¹⁴And R¹⁵In the above, examples of alkyl groups include
Includes chill, ethyl and butyl. Of the alkoxy group
Examples include methoxy and ethoxy. Carboki
Examples of salts of sil or sulfo groups include sodium salts and
And ammonium salts. R of the formula (III-1)¹¹In the above, an aryl group
Examples include phenyl and naphthyl. Haloge
Examples of chlorine atoms include chlorine and bromine. Formula (III−
2) R¹³, R¹⁴And R¹⁵In the example of the amide group
Includes acetamide and benzamide. Cal
Examples of bamoyl groups include ethylcarbamoyl and phenyl.
And rucarbamoyl. Examples of sulfonamide groups
Is methanesulfonamide and benzenesulfonamide
Is included. The above alkyl group, alkoxy group, aryl
Group, amino group, amide group, carbamoyl group and sulfo group
The honamide group may further have a substituent. example
For example, amino groups substituted with alkylcarbamoyl groups,
That is, the alkyl-substituted ureido group is also included in the substituted amino group.
You. [0040] Embedded image Wherein Z is -NR¹⁶-, Oxygen atom or sulfur
It is a yellow atom. R¹⁷Represents a hydrogen atom, an alkyl group,
Group, alkenyl group, cycloalkyl group, -SR¹⁸, −
NR¹⁹R²⁰, -NHCOR^{twenty one}, -NHSO_Two R^{twenty two}Or
It is a heterocyclic group. R¹⁶And R¹⁸Is hydrogen
Atom, alkyl group, alkenyl group, cycloalkyl group,
Aryl group, -COR^{twenty three}Or -SO_Two R^{twenty four}It is. R
¹⁹And R²⁰Represents a hydrogen atom, an alkyl group or
Is an aryl group. R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}Is
Each is an alkyl group or an aryl group. M is a click
Is on. R of the formula (III-3)¹⁶, R¹⁷, R¹⁸, R¹⁹,
R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}In the alkyl
Examples of groups include methyl, benzyl, ethyl and propyl
Is included. Examples of aryl groups include phenyl and naph
Includes chill. R of the formula (III-3)¹⁶, R¹⁷And R¹⁸
In, an example of an alkenyl group is propenyl. Shiku
An example of a loalkyl group is cyclohexyl. Formula (III−
3) R¹⁷In the above, examples of the heterocyclic group include furyl and
And pyridinyl. The above alkyl group and aryl
Group, alkenyl group, cycloalkyl group and heterocyclic group
May further have a substituent. For example, an aryl group
Also substituted alkyl group, that is, aralkyl group
Included in alkyl groups. [0043] Embedded image Where R^{twenty five}Is R in the formula (III-3)¹⁷
Has the same definition as M is a cation. R²⁶And
And B²⁷Is R in formula (III-3)¹⁶and
R¹⁹Has the same definition as In the following, the formula (III)
Specific examples of the compounds to be prepared are shown below. [0045] Embedded image [0046] Embedded image [0047] Embedded image [0048] Embedded image[0049] Embedded image [0050] Embedded image [0051] Embedded image [0052] Embedded image [0053] Embedded image [0054] Embedded image [0055] Embedded image[0056] Embedded image [0057] Embedded image [0058] Embedded image [0059] Embedded image [0060] Embedded image [0061] Embedded image [0062] Embedded image [0063] Embedded image [0064] Embedded image [0065] Embedded image[0066] Embedded image [0067] Embedded image [0068] Embedded image [0069] Embedded image [0070] Embedded image [0071] Embedded image [0072] Embedded image [0073] Embedded image[0074] Embedded image [0075] Embedded image [0076] Embedded image The addition amount of the mercaptoheterocyclic compound is
1 × 10 per mole of silver logenide^-Five~ 5 × 10^-2Mole
And preferably 1 × per mole of silver halide.
10^-Four~ 1 × 10^-2More preferably, it is molar.
Regarding the addition method to the surface latent image type silver halide emulsion layer,
There is no particular limitation. Physical ripening during silver halide grain formation
Medium, during chemical ripening, or during coating solution preparation.
Can be. The surface latent image type silver halide emulsion layer was
It preferably contains an azaindene compound. Preferred Te
The triazaindene compounds are represented by the following formulas (IV) and (V)
Is represented by [0079] Embedded image [0080] Embedded image Where R³¹, R³², R³³, R³⁴, R⁴¹, R
⁴², R⁴³And R⁴⁴Is a hydrogen atom, an alkyl
Group, aryl group, amino group, hydroxy group, alkoxy
Group, alkylthio group, carbamoyl group, halogen atom,
Cyano group, carboxyl group, alkoxycarbonyl group
Or a heterocyclic group. R³¹And R³², R³²And R³³, R⁴¹
And R⁴²Or R⁴²And R⁴³Are linked to form a 5- or 6-membered ring
It may be formed. Where R³¹And R³³At least
One represents a hydroxy group. Similarly, R⁴¹And R⁴³Baby
Wherein at least one represents a hydroxy group The above alkyl group is branched even if it is cyclic.
You may have. The number of carbon atoms in the alkyl group is 1 to
It is preferably 20. Carbon source of the above alkoxy group
The number of children is preferably 1 to 20. The above archi
The number of carbon atoms of the luthio group is preferably 1 to 6.
No. The number of carbon atoms in the alkoxycarbonyl group is 2 to
It is preferably 20. The heterocyclic group may have up to 5 members
It preferably has a 6-membered ring. Heterocyclic group
Examples of b atoms include nitrogen, oxygen and sulfur
A child can be mentioned. The above alkyl group and aryl
Group, amino group and carbamoyl group further have a substituent.
May have. Examples of the substituent include an aliphatic group and an aromatic group.
Groups. Tetraazaindene compounds are polymers
May be formed. Repeating units of such polymers
Is represented by the following formula (VI). [0083] Embedded image Where R⁵¹Is a hydrogen atom or an alkyl group
And X is a compound represented by the formula (IV) or (V)
J is a monovalent group excluding one hydrogen atom.
It is a group. For X, the above formula (IV) or (V)
R in³¹, R³², R³³, R³⁴, R⁴¹, R⁴², R⁴³Ma
Or R⁴⁴One hydrogen atom may be removed from the portion. The formulas (IV), (V) and (VI)
Examples of alkyl groups include methyl, ethyl, n-propyl, is
o-propyl, n-butyl, iso-butyl, tert-butyl,
Hexyl, cyclohexyl, cyclopentylmethyl,
Contains octyl, dodecyl, tridecyl, heptadecyl
You. Examples of the substituent of the alkyl group include an aryl group and a hetero group.
Ring group, halogen atom, carboxy group, alkoxycarbo
Nyl group (preferably having 2 to 6 carbon atoms), alkoxy
Di-groups (preferably having 19 or less carbon atoms)
Xyl groups are included. Examples of substituted alkyl groups include benzyl
, Phenethyl, chloromethyl, 2-chloroethyl,
Trifluoromethyl, carboxymethyl, 2-carboxy
Ethyl, 2- (methoxycarbonyl) ethyl, ethoxy
Carbonylmethyl, 2-methoxyethyl, hydroxymethyl
Includes tyl and 2-hydroxyethyl. Examples of aryl groups include phenyl and naph
Includes chill. Examples of the substituent of the aryl group include alkyl
Group (preferably having 4 or less carbon atoms), halogen source
Child, carboxy group, cyano group, alkoxycarbonyl group
(Preferably having 6 or less carbon atoms), a hydroxy group and
And alkoxy groups (preferably having 6 or less carbon atoms).
I will. Examples of substituted aryl groups include p-tolyl, m-to
Ryl, p-chlorophenyl, p-bromophenyl, o-
Chlorophenyl, m-cyanophenyl, p-carboxy
Phenyl, o-carboxyphenyl, o- (methoxyca
Rubonyl) phenyl, p-hydroxyphenyl, p-meth
Toxinphenyl and m-ethoxyphenyl
You. Examples of the substituent of the amino group include an alkyl group (eg, methyl
, Ethyl, butyl), acyl groups (eg, acetyl, pro
Pionyl, benzoyl) and sulfonyl groups (eg, meta
And sulfonyl). Examples of substituted amino groups include di
Methylamino, diethylamino, butylamino and amino
Cetamide is included. Examples of the alkoxy group include methoxy and ethoxy.
Si, butoxy and heptadecyloxy. A
Examples of alkylthio groups include methylthio, ethylthio and
Hexylthio is included. Examples of carbamoyl group substituents
Has an alkyl group (preferably having 20 or less carbon atoms)
And an aryl group (preferably phenyl or naphthyl)
Le). Examples of substituted carbamoyl groups include methyl
Carbamoyl, dimethylcarbamoyl, ethylcarbamo
And phenylcarbamoyl. Alkoki
Examples of the carbonyl group include methoxycarbonyl and ethoxy.
Includes carbonyl and butoxycarbonyl. C
Examples of logen atoms include fluorine, chlorine and bromine
Atoms are included. A heterocyclic group is a fused ring of two or three rings
May be formed. Examples of heterocyclic groups include furyl and pyri.
Jill, 2- (3-methyl) benzothiazolyl and 1-
Includes benzotriazolyl. R³⁴Or R⁴⁴Replace
In the alkyl group, when the substituent is a heterocyclic group,
The substituent represented by the following formula (VII) is preferred. [0088] Embedded image Where R⁶¹, R⁶²And R⁶³Is the formula (IV)
R in³¹, R³²And R³³Has the same definition as
n is 2, 3 or 4. Next, equations (IV), (V) and
Specific examples of the compounds represented by any of (VI) and (VI)
You. [0090] Embedded image [0091] Embedded image [0092] Embedded image[0093] Embedded image [0094] Embedded image [0095] Embedded image [0096] Embedded image [0097] Embedded image [0098] Embedded image [0099] Embedded image[0100] Embedded image [0101] Embedded image [0102] Embedded image [0103] Embedded image [0104] Embedded image [0105] Embedded image [0106] Embedded image[0107] Embedded image [0108] Embedded image [0109] Embedded image [0110] Embedded image [0111] Embedded image [0112] Embedded image The addition amount of the tetraazaindene compound is
1 × 10 per mole of silver logenide^-Five~ 3 × 10^-1Mole
And preferably 3 × 10^-Four~ 1 × 10^-1Mole
Is more preferable. The addition amount is
Size of silver halide emulsion, halogen composition, chemical sensitization
Method and degree, the relationship between surface latent image type emulsion layer and other
Depends on the type of inhibitory compound. Because of this, the optimal amount
Is desirably selected experimentally. Tetraazaine
By adding a den compound to the silver halide emulsion,
The compound can be easily included in the silver halide emulsion layer.
Wear. Compound in the non-photosensitive hydrophilic colloid layer
When adding the compound, add the compound to the coating solution for the non-photosensitive layer.
do it. Compounds are preferably added in solution.
New Water and organic solvents are used as the solvent for the solution.
It is. Preferably, the organic solvent is miscible with water. Yes
Examples of organic solvents include alcohols (eg, methanol, ethanol
), Esters (eg, ethyl acetate) and ketones
(Eg, acetone). Tetraazaindene conversion
The compound may be well dissolved in the alkaline aqueous solution.
In that case, it is convenient to use an alkaline aqueous solution.
You. Tetraazaindene compound in silver halide emulsion
When added, a halo is formed from the step of forming silver halide grains.
It can be added at any time before the coating process
is there. Preferably after the start of the chemical ripening process,
It is more preferable to add it after completion of the process and before coating.
Good. A cyanochrome complex ion is converted to a silver halide grain.
Dope, the effect is hard and sharp on the sole
Fruit is obtained. There, mercaptoheterocyclic compounds and te
Addition of a triazaindene compound further preserves the life
And the maximum optical density is improved. Mercaptoheterocycle
Compounds and compounds of tetraazaindene compounds
Even if either one of the compounds is used, a sufficient effect can be obtained.
Two or more compounds may be used in combination for each.
No. In addition, mercaptoheterocyclic compounds and tetraazain
You may use together with a den compound. The silver halide grains have a silver chloride content of 50%.
It is preferable to have a halogen composition that is at least
Good. The silver chloride content must be at least 80 mol%.
And more preferably 90 mol% or more.
No. In the present invention, the silver chloride content is 50 mol% or more.
Silver chloride, silver chlorobromide or silver chloroiodobromide grains
You. In particular, silver chlorobromide containing substantially no silver iodide or
Preferably using silver halide grains composed of silver chloride
Can be. When grains containing substantially no silver iodide are used,
The development processing time can be reduced. Practically silver iodide
Not containing a silver iodide content of 1 mol% or less
Or less than 0.2 mol%. High silver chloride
C. with 0.01 to 3 mol% of silver iodide introduced on the surface of the grains
A logen composition may be employed. Such a halogen group
To increase sensitivity to high illumination, to increase spectral sensitization sensitivity,
Or to improve the aging stability of the photosensitive material.
(Described in JP-A-3-84545). emulsion
May be different between grains. Between particles
When using an emulsion having the same halogen composition as
It is easy to homogenize the properties of Halogen composition inside silver halide emulsion grains
Regarding the distribution, particles with a uniform structure and particles with a non-uniform structure
is there. In silver halide grains having a uniform structure,
Even if a part is taken, the composition becomes equal. For particles with heterogeneous structure
Is the core inside the silver halide grain and the shell surrounding it.
And halogen composition (including the composition of multiple layers)
There are particles having a laminated structure. For particles of other heterogeneous structures
Has a different halogen composition non-layered inside or on the surface of the grains.
(Particle surface has particle edges, core
Structure in which different composition parts are joined on the surface or surface)
Particles having the formula: To obtain high sensitivity, uniform
Any heterogeneous structured particles are preferred over structured particles
Used for Are particles with a heterogeneous structure a point of pressure resistance?
Are also preferred. Silver halide grains have heterogeneous structure
In some cases, the boundary between different parts in the halogen composition
Is an unclear boundary where a mixed crystal is formed due to a composition difference.
You may. In addition, active structural changes at the boundary
May be introduced. In the high silver chloride emulsion, the silver bromide localized phase
In a layered or non-layered form as described above.
A structure having the inside or surface of the child is preferred. Above localized phase
Has a silver bromide content of 10 mol% or more.
And more preferably more than 20 mol%.
Good. The silver bromide content of the silver bromide localized phase was determined by X-ray diffraction.
(For example, The Chemical Society of Japan, “New Experimental Chemistry Course 6 Structural Solution
Analysis (described in Maruzen)).
The localized phase can be located inside the particle, at the edge, corner, or
Can be introduced on the surface. The localized phase is
It is particularly preferable to perform epitaxial growth on the corner portion.
In order to reduce the replenishment amount of the developing solution, silver halide milk
It is also effective to increase the silver chloride content of the agent. in this case
Has a silver chloride content of 98 mol% to 100 mol%
Emulsions that are substantially pure silver chloride are also preferably used. The average grain size of the silver halide grains is as follows:
It is preferably in the range of 0.1 to 2 μm. Average grain
Is the diameter of the circle equivalent to the projected area of each particle.
The particle size means its number average. Particle size
Is preferably monodisperse. In particular,
Coefficient of variation (= standard deviation of particle size distribution ÷ average particle size
Is preferably 20% or less, and 15% or less.
More preferably, it is most preferably 10% or less.
Is also preferred. In order to obtain a wide latitude,
Dispersion emulsions may be mixed and used in the same layer. Similar eyes
Alternatively, a plurality of monodispersed emulsions may be coated in a multilayer manner. Haloge
Silver halide grains can be cubic, tetrahedral or octahedral
Having a regular crystalline form, such as a body, a sphere
Irregular (irregular) crystal form
And those having a composite form of these
You. In addition, emulsions having various crystal forms are mixed.
May have a different configuration. In the present invention, the above-mentioned regular
50% or more of particles having various crystal forms are preferred.
And more preferably 70% or more.
% Is most preferable. Silver halide emulsion
Exceeds 50% of all grains with projected area of tabular grains
May be included. Tabular grains generally have an aspect ratio
(Circular diameter / thickness) is 5 or more, preferably 8 or more
Above. Purpose of preparing monodispersed silver halide emulsion
And a silver halide solvent can be used. halogen
Examples of silver halide solvents include thiocyanates and thioether compounds.
Substances, thioureas, thione compounds, amine compounds, rhodane
Potash and Rodin Ammon are included. Thiocyanate, thi
Oether compounds and thioureas are preferred. Also,
Ammonia can be used together as long as there is no adverse effect.
Wear. For thiocyanates, see U.S. Pat.
Nos. 64, 2448534 and 3320069
It is described in each specification. About thioether compounds
Are U.S. Pat. Nos. 3,271,157 and 3,574,628;
No. 3704130, No. 4276347 and No. 42
No. 97439. About thione compounds
And JP-A-53-82408 and JP-A-53-1443.
Nos. 19 and 55-77737.
Amine compounds are described in JP-A-54-100717.
It is described in the gazette. The silver halide emulsion can be prepared by a known method.
Can be built. Generally, has an aqueous gelatin solution
The silver salt aqueous solution and the
An aqueous halide solution is added. About specific method
Was written by P. Glafkides, "Shimmy
Chimie et Phys
ique Photographeque) "(Paul Monell
tel), 1967), GF Duffin (G.
F.Duffin), "Photographic Emulsion
Chemistry (Photographic Emulsion Chemistry) "
(Focal Press, 1966) and V.L.
・ Making a book by V.L.Zelikman et al.
Coating Photographic Emarjo
(Making and Coating Photographic Emulsion) "
(Focal Press, 1964). acid
Any of neutral method, neutral method and ammonia method can be adopted
You. Form of reacting soluble silver salt with soluble halide
The one-sided mixing method, the simultaneous mixing method,
Either may be used. Halogenation is one type of simultaneous mixing method.
A method for maintaining a constant pAg in a liquid phase in which silver is formed,
In other words, the controlled double jet method can be used.
it can. In addition, the specification of British Patent No.
48-48890 and 52-16364
As described in the report, silver nitrate and
Change the addition rate of the aqueous solution according to the particle formation rate
Is also good. U.S. Pat. No. 4,242,445 and JP
As described in U.S. Pat.
Exceeding critical supersaturation using a method that changes solution concentration
It is preferable to grow as quickly as possible within a range that does not exist. this
According to these methods, renucleation does not occur, and silver halide
The particles grow uniformly. During the formation of silver halide grains, grain growth
To control the silver halide solvent described above
Can be used. Silver halide grain formation or material
Cadmium salts, zinc salts, tariu
Salt, iron salt or its complex, ruthenium salt or its complex
Salt, osmium salt or its complex salt, cobalt salt or its salt
Complex salts, rhodium salts or their complex salts, iridium salts or
May coexist with a complex salt thereof. Inside the particle (core
Part) and the outer part (shell part), so-called double structure grains
A child may be formed. In addition, triple structure particles and more
(Japanese Patent Application Laid-Open No. 60-22284)
May be formed. Introduce structure inside emulsion grains
In addition to the above-mentioned wrapping structure,
Particles having a bonding structure can also be formed. Joining
Regarding particles having a structure, see JP-A-58-10852.
No. 6, No. 59-16254, No. 59-133540
And Japanese Patent Publication No. 58-24772 and European Patent
No. 199, 290A2. The crystal to be bonded is different from the host crystal.
The composition has The junction crystal is located at the edge or core of the host crystal.
It is generated by bonding to the toner or the surface. This
Such a bonded crystal has a structure in which the host crystal has a uniform halogen composition.
Even one can be formed. In case of joint structure
In addition to the combination of silver halide,
Halogen-free silver salt compounds such as silver and silver carbonate
A bonding structure can be obtained in combination with silver halide. Also,
Non-silver salt compounds such as PbO can also have a junction structure.
In some cases. Silver iodobromide grains having a core-shell structure
In the grain of the particle, the core part has a high silver iodide content
It can be. Conversely, the shell part has a silver iodide content
It is also possible to make it a structure with high. Similarly, the joint structure
Regarding the particles having, also the silver iodide content of the host crystal
High and relatively low silver iodide content of the bonded crystal
Structures and vice versa are possible. These structures
The different boundary portions of the halogen composition of grains having
A mixed crystal may be formed due to the difference and the boundary may be unclear.
Further, a continuous structural change may be positively introduced. The silver halide emulsion causes grain roundness.
Treatment (European Patents 96727B1 and 64412)
B1). Also, in the emulsion
Surface modification treatment (German Patent No. 2306447C2)
And JP-A-60-221320).
May be. Dislocation lines may be introduced into silver halide grains.
No. Silver halide grains having dislocation lines are disclosed in US Pat.
No. 06461. A binder for an emulsion layer or an intermediate layer of a light-sensitive material or
Gelatin is advantageously used as a protective colloid.
A hydrophilic polymer other than gelatin may be used. Other parents
Examples of aqueous polymers include proteins (eg, gelatin-derived
Body, graft polymer of gelatin and other macromolecules,
Bumin, casein), sugar derivatives (eg, cellulose derivatives)
Body, sodium alginate, starch derivative) and synthetic hydrophilicity
Polymers (eg, polyvinyl alcohol, polyvinyl alcohol
Coal partial acetal, poly-N-vinylpyrrolidone,
Polyacrylic acid, polymethacrylic acid, polyacrylamide
, Polyvinyl imidazole, polyvinyl pyrazole,
Copolymers thereof). Above cellulo
Examples of glucose derivatives include hydroxyethylcellulose,
Ruboxyl methyl cellulose and cellulose sulfate
Included. General-purpose lime-processed gelatin is used as gelatin.
Using acid-treated gelatin or enzyme-treated gelatin in addition to chin
May be. Enzyme-treated gelatin is the journal of the Japan Society of Science Photography
(Bull. Soc. Photo. Japan), 16
Vol. 30, 30 (1966). Add gelatin
Hydrolysates are also available. Hydrophilicity constituting photographic layer or back layer
Even if an inorganic or organic hardener is added to the colloid layer,
Good. Hardening agents include chromium salts, aldehyde salts, N-
Methylol compounds, active halogen compounds, active vinylation
Compounds, N-carbamoylpyridinium salts and haloas
Midinium salts are available. Active halogen compounds, active
Vinyl compounds, N-carbamoylpyridinium salts and the like
And haloamidinium salts are preferred due to their faster curing speed.
New Active halogen compounds and active vinyl compounds are
It is more preferable to provide more stable photographic characteristics.
Examples of aldehydes that constitute aldehyde salts include formaldehyde
Aldehyde, glyoxal and glutaraldehyde
included. Examples of N-methylol compounds include dimethylol
Luurea. Examples of active halogen compounds include 2,4-
Dichloro-6-hydroxy-1,3,5-triazine and
And its sodium salt. Active vinyl compounds
Examples include 1,3-bisvinylsulfonyl-2-propano
, 1,2-bis (vinylsulfonylacetamide)
Ethane, bis (vinylsulfonylmethyl) ether and
Vinyl polymer having vinyl and vinyl sulfone groups in the side chain
included. Examples of N-carbamoylpyridinium salts include:
(1-morpholinocarbonyl-3-pyridinio) methane
Sulfonate. Examples of haloamidinium salts are 1
-(1-chloro-1-pyridinmethylene) pyrrolidinium
This is the Mo2 Naphthalene Sulhot. The silver halide emulsion is generally spectrally sensitized.
You. Methine dyes, cyanine colors as spectral sensitizing dyes
Element, merocyanine dye, complex cyanine dye, complex melody
Anine dye, holopolar cyanine dye, hemicyanine
Uses dyes, styryl dyes and hemioxonol dyes
it can. Cyanine dyes, merocyanine dyes and complex
Russianin dyes are particularly useful. It's a cyanine dye
Such spectral sensitizing dyes generally have a basic heterocycle.
Examples of the hetero ring include a pyrroline ring, an oxazoline ring, and a thia ring.
Zoline ring, pyrrole ring, oxazole ring, thiazole
Ring, selenazole ring, imidazole ring, tetrazole ring
And a pyridine ring. These rings have an aliphatic ring
Alternatively, an aromatic ring may be condensed. Examples of fused rings include
Nrenren ring, benzindolenin ring, indole ring,
Benzoxadol ring, naphthoxazole ring, benzo
Thiazole ring, naphthothiazole ring, benzoselenazo
Ring, benzimidazole ring and quinoline ring
You. Even if these rings have a substituent on a carbon atom,
Good. Merocyanine dye or complex merocyanine dye
The ring is a 5- or 6-membered heterocycle having a ketomethylene structure.
It is a ring. Examples of rings having a ketomethylene structure include
Lazoline-5-one ring, thiohydantoin ring, 2-thio
Oxazolidine-2,4-dione ring, thiazolidine-
2,4-dione ring, rhodanine ring and thiobarbitu
Includes a phosphoric acid ring. Using two or more sensitizing dyes in combination
You may. Combinations of sensitizing dyes are particularly useful for supersensitization.
Often used. Using a supersensitizer with a sensitizing dye
You may. Supersensitizers have their own spectral sensitizing effect
Dyes or substances that do not substantially absorb visible light
You. Examples of supersensitizers include those substituted with a nitrogen-containing heterocyclic group.
Aminostilbenzene compounds (US Pat. No. 2,933,339)
Nos. 0 and 3635721), aromatic
Condensates of organic acids and formaldehyde (U.S. Pat.
No. 510), cadmium salts and azaindenes
Compounds. About combinations of sensitizing dyes
Are U.S. Pat. Nos. 3,615,613 and 3,615,641;
Nos. 3,617,295 and 3,635,721
There is a description. The halide emulsion is generally chemically sensitized.
Chemical sensitization includes sulfur sensitization, selenium sensitization, tellurium sensitization, and precious gold
Perform genus sensitization, reduction sensitization or a combination thereof
You. In sulfur sensitization, silver sulfide reacts with silver ions to form silver sulfide.
Using unstable sulfur compounds that can be generated as sulfur sensitizers
You. See P. Glafkides, Chimie e, for sulfur sensitization.
t Physique Photographeque ”(Paul Montel, 1
987, 5th edition), Research Ticlosure, 3
07105, edited by T.H.James, "The Theory of the
Photographic Process, ”published by Macmillan, 1977
Year, 4th Edition), and H. Frieser, "Die Grundlagen
der Photographischen Prozess mit Silver-halogenide
n "(Akademische Verlagsgeselbshaft, 1968)
There is a description. Examples of sulfur sensitizers include thiosulfates (eg,
Sodium thiosulfate, p-toluenethiosulfone
G), thioureas (eg, allylthiourea, N, N'-di
Phenylthiourea, triethylthiourea, acetylthio
Urea, N-ethyl-N '-(4-methyl-2-thiazoly
Thiourea), thioamides (eg, thioacetamido)
, N-phenylthioacetamide), rhodanines
(E.g., rhodanine, N-ethylrhodanine, 5-benzy
Ridenredanine, 5-benzylidene-N-ethyl-b
-Danine, diethylrhodanine), thiohydantoin
, 4-oxo-oxazolidine-2-thiones, diss
Sulfides, polysulfides, thiosulfonic acids,
Mercapto compounds (eg, cysteine), polythioic acid
Includes salts, elemental sulfur and sodium sulfide. one
Generally, thiosulfates, thioureas, thioamides and
And rhodanins are used. In selenium sensitization, an unstable selenium compound
Is used as a selenium sensitizer. About selenium sensitization
Are JP-B-43-13489 and 44-15748.
JP-A-4-25832, JP-A-4-40324,
4-109240, 4-147250 and 4
-2711341.Selenium sensitizer
Examples include selenoureas (eg, selenourea, N, N-dimene).
Tylselenourea, N, N-diethylselenourea, tetra
Methylselenourea, N, N, N'-trimethyl-N'-
Acetylselenourea, N, N, N'-trimethyl-N '
-Heptafluoropropylcarbonylselenourea, N,
N, N'-trimethyl-N'-4-chlorophenylcar
Bonyl selenourea, N, N, N'-trimethyl-N'-
4-nitrophenylcarbonylselenourea), selenoa
Amides (eg, selenoacetamide, N, N-dimethylse
Renobenzamide), selenoketones (eg, selenoace
Ton, selenoacetophenone, bis- (adamantyl)
Selenoketone), isoselenocyanates (eg, allyl)
Isoselenocyanate), selenocarboxylic acids and
Esters (eg, selenopropionic acid, methyl-3-se
Lenobutyrate), selenides (eg, dimethyl selena)
Id, diethyl selenide, triphenylphosphine
Selenide), selenophosphates (eg, tri-p
-Tolyl selenophosphate) and colloidal metals
Contains selenium. Regarding tellurium sensitization, see US Pat.
499, 3320069, 3772031,
British Patent Nos. 235211, 1121496, 12
Nos. 95462, 1396696 and Canadian Patent 8
00958 each specification, Journal of Chemical
Society Chemical Communication (J.Ch
em. Soc., Chem. Commun.), 635 (1980), 11
02 (1979), 645 (1979), Journal
・ Chemical Society Parkinson To
Transactions (J. Chem. Soc., Perkin. Trans.) 1, 2
191 (1980), JP-A-4-204640 and
It is described in JP-A-4-330430. Tellurium sensitization
Examples of agents include colloidal tellurium, telluroureas (eg, a
Riltellurourea, N, N-dimethyltellurourea, tetra
Methyltellurourea, N-carboxyethyl-N ', N'
-Dimethyltellurourea, N, N'-dimethylethylenete
Lulureas, N, N'-diphenylethylene tellurouria
Element), isotellurocyanates (eg, allyl isostero
Cyanate), telluro ketones (eg, telluroacetone,
Telluroacetophenone), telluroamides (eg, telluro
Acetamide, N, N-dimethyltellurobenzami
), Tellurohydrazide (eg, N, N ', N'-trime
Tiltellobenzhydrazide), telluroester (eg,
t-butyl-t-hexyltelluroester), phosphine
Intertellides (eg, tributylphosphine telluride,
Licyclohexylphosphine telluride, triisopropyl
Ruphosphine telluride, butyl-diisopropylphosphine
Intertellide, dibutylphenylphosphine telluride
), Gelatin containing negatively charged telluride ions (UK special
No. 1295462), potassium tellurium
Do, potassium tellurocyanate, telluropentathione
Contains sodium salt and allyl terocyanate
It is. In the noble metal sensitization, gold, platinum, palladium
Noble metal sensitization of noble metal compounds such as uranium and iridium
Used as an agent. For precious metal sensitization, see P. Grafkide
s, Chimie et Physique Photographique (Paul
 Montel, 1987, 5th edition) and Research
No. 307105. Money increase
The feeling is particularly preferred. Examples of gold sensitizers include chloroauric acid, potassium
Um chloroaurate, potassium aurithiocyanate
G, gold sulfide and gold selenide. Gold sensitizer
Are U.S. Pat. Nos. 2,642,361 and 5,049,484;
It is described in each specification of JP 5049485. In the reduction sensitization, a reducing compound is reduced
Used as a sensitizer. For reduction sensitization, see P. Grafkide
s, Chimie et Physique Photographique (Paul
 Montel, 1987, 5th edition) and Research
Ticlosure, 307, 307105
You. Examples of reduction sensitizers include aminoiminomethane sulfide
Acid (= thiourea dioxide), borane compound (eg, dimethyl
Luamine borane), hydrazine compounds (eg, hydrazine
, P-tolylhydrazine), a polyamine compound (eg,
Diethylenetriamine, triethylenetetramine), salt
Stannous chloride, silane compounds, reductones (eg, Asco
Rubic acid), sulfites, aldehyde compounds and hydrogen gas
Included. Performed by combining two or more types of chemical sensitization
May be. Combinations include chalcogen sensitization (sulfur sensitization)
Sensitization, selenium sensitization, tellurium sensitization) and gold sensitization
Good. Reduction sensitization is performed during silver halide grain formation
Is preferred. The amount of chalcogen sensitizer used is
10 per mole of silver logenide^-8To 10^-2In the mole range
Preferably, 10^-7~ 5 × 10^-3Mole range
Is more preferable. Noble metal sensitizer usage
Is 10 per mole of silver halide^-7-10^-2Molar range
It is preferred that it is an enclosure. Conditions for chemical sensitization include p
Ag is preferably in the range of 6 to 11, and 7 to
More preferably, it is in the range of 10. pH is 4
It is preferably in the range of 10 to 10. The temperature is between 40 and
It is preferably in the range of 95 ° C,
More preferably, it is within the range. The silver halide photographic emulsion further includes various types of
Compounds can be added. These compounds are
Prevents fogging from manufacturing and storage of optical materials to photographic processing
Alternatively, it can be added for the purpose of stabilizing photographic performance. these
Examples of additives include azoles (eg, benzothiazoliu
Salt, nitroimidazoles, nitrobenzimidazo
Chlorobenzimidazoles, bromobenzimid
Dazoles), mercaptopyrimidines, mercaptoto
Liazines, thioketo compounds (eg, oxazoline thio
Azaindenes (eg, triazaindenes, pens
Taazaindenes), benzenethiosulfonic acid, ben
Zensulfinic acid and benzenesulfonamide
included. Addition of surfactant to photosensitive material
Can be. Surfactants aid in application, antistatic,
Improvement of resilience, emulsification and dispersion, prevention of adhesion and improvement of photographic properties
(Eg, development acceleration, high contrast, sensitization)
used. The silver halide grains are the same as those of the present invention.
Iron, ruthenium and osmium in addition to the complex ions
Other, such as cobalt, cobalt, rhodium or iridium
A metal complex can be included. Two or more complexes
May be used in combination with the cyanochrome complex ion. Money
The addition amount of the complex of the genus is 10 per mole of silver halide.^-9No
To 10^-2Molar range, preferably halogenated
10 per mole of silver^-8To 10^-FourMole range
Is more preferred. Iron, ruthenium, osmium, koba
Metal complexes of ortho, rhodium or iridium are halogenated
Preparation of silver halide grains (nucleation, growth, physical ripening, chemical
Before and after sensitization). Metal complex several times
It may be added in portions. The metal complex can be dissolved in water or organic
It can be added by dissolving in a medium. Organic solvent mixed with water
It is preferable to have compatibility. Examples of organic solvents include
Coals, ethers, glycols, ketones, S
Includes ters and amides. Metal complex used in combination with cyanochrome complex ion
Is particularly preferably an iridium complex. iridium
The complex is preferably trivalent or tetravalent. Iriji
Hexachloroiridium (III) complex
Salt, hexachloroiridium (VI) complex salt, hexabromo
Iridium (III) complex salt, hexabromoiridium (VI)
Complex salt, hexaiodoiridium (III) complex salt, hexayo
Doridium (VI) complex salt, hexaammine iridium (I
II) Complex salt and hexaammineiridium (VI) complex salt
included. The counter cation of the iridium complex is miscible with water
And is suitable for the precipitation operation of silver halide emulsions.
It is preferable to use ON. Examples of counterions include al
Potassium metal ion (eg, sodium ion, potassium ion
, Rubidium ion, cesium ion, lithium ion
), Ammonium ion and alkyl ammonium
Ions are included. About alkyl ammonium ion
The above has been described with reference to the formula (II). Addition of iridium complex
The amount is a hexacyanoiridium complex represented by the following formula (VII):
, Except for the case of^-9Or
10^-FourMolar range, preferably silver halide
10 per mole^-8To 10^-FiveTo be in the molar range
More preferred. Metal complex used in combination with cyanochrome complex ion
Is a hexacyano metal complex represented by the following formula (VII):
Particularly preferred. Hexacyano metal complex is a highly sensitive photosensitive material
And even when the raw photosensitive material is stored for a long period of time
This has the effect of suppressing the occurrence of fogging. (VII) [M (CN)₆ ]^n- Where M is iron, ruthenium, osmium, cobalt, b
N or 3 or 4
You. Specific examples of the hexacyano metal complex are shown below. (VII-1) [Fe (CN)₆ ]^Four- (VII-2) [Fe (CN)₆ ]^3- (VII-3) [Ru (CN)₆ ]^Four- (VII-4) [Os (CN)₆ ]^Four- (VII-5) [Co (CN)₆ ]^3- (VII-6) [Rh (CN)₆ ]^3- (VII-7) [Ir (CN)₆ ]^3- The counter cation of the hexacyano complex is miscible with water.
And is suitable for the precipitation operation of silver halide emulsions.
It is preferable to use ON. Examples of counterions include al
Potassium metal ion (eg, sodium ion, potassium ion
, Rubidium ion, cesium ion, lithium ion
), Ammonium ion and alkyl ammonium
Ions are included. About alkyl ammonium ion
The above has been described with reference to the formula (II). The addition amount of the hexacyano metal complex depends on the amount of halogenated
10 per mole of silver^-6To 10^-3Mole range
And preferably 5 × 10 5 per mol of silver halide.^-6Or
5 × 10^-FourMore preferably, it is in the molar range.
Iron, ruthenium, osmium, cobalt, rhodium or
Is the hexacyano metal complex of iridium, silver halide grains
Preparation stage (before nucleation, growth, physical ripening, chemical ripening)
Later). Hexacyano metal complex
It may be added in several portions. Iron, ruteniu
, Osmium, cobalt, rhodium or iridium
The hexacyano metal complex of the present invention accounts for 50% or more of the total
Preferably, it is introduced into a surface phase of 50% or less of the volume.
Here, the surface phase of 50% or less of the particle volume means one particle.
Means a surface portion corresponding to a volume of 50% or less of the volume of
You. The volume of this surface phase is preferably 40% or less.
And more preferably 20% or less. Also here
Iron, ruthenium and osmium outside the defined surface phase
Hexagonal gold of cobalt, rhodium or iridium
A layer that does not contain a metal complex may be provided. Iron, ruteniu
, Osmium, cobalt, rhodium or iridium
Hexacyano metal complex is water or an organic solvent miscible with water.
Dissolve in the reaction medium to form the silver halide grains in the reaction solution.
Can be added directly. Or silver halide grains
Solution for the formation of electrons (in silver halide solution, silver water
Solution) or any other solution
The particles can be introduced by forming particles.
In addition, silver halide grains containing a metal complex in advance are dissolved.
Solution, add and deposit on another silver halide grain.
Can also introduce metal complexes into the particles.
You. The coating pH of the silver halide photographic material is
It is preferably from 4.0 to 6.5, and more preferably from 5.0 to 6.5.
More preferably, it is 6.5. Coating pH
All constituent layers obtained by applying the liquid on the support
PH. For this reason, the coating pH is different from the pH of the coating solution.
Do not always match. The coating pH is measured by the following method
can do. (1) Table of photosensitive material on the side coated with silver halide emulsion
0.05 ml of pure water is dropped on the surface. next, (2) After standing for 3 minutes, a film pH measurement electrode (G
S-165F) to measure the coating pH. The above method is described in JP-A-61-245153.
There is. The coating pH can be acid (eg, sulfuric acid, citric acid) or
Alkali (eg, sodium hydroxide, potassium hydroxide)
It can be adjusted using. Addition of acid or alkali
There is no particular limitation on the method. As for the time of addition,
It is easiest to carry out when preparing the coating solution. Acid or
Is added to some of the photographic constituent layers.
May be. The hydrophilic colloid layer of the light-sensitive material can be decolorized.
A functional dye may be added. Such dyes are
Prevention of radiation and halation and safelight
Can be used for the purpose of improving safety. Decolorizable dye
Examples include oxonol and cyanine dyes
It is. Regarding decolorizable dyes, EP 33,749
It is described on page 27-76 of the specification of 0A2. Fix the dye
In the state of body particle dispersion, it is added to the hydrophilic colloid layer,
Decolorization may be performed by image processing. For such dyes,
JP-A-2-282244, pages 3 to 8, and JP-A-2-282244.
It is described on pages 3 to 11 of JP-A-3-7931. Other
May be added to the photosensitive material. Examples of other dyes
Include hemioxonol dyes, styryl dyes, merocyanines
Nin dye, anthraquinone dye, azo dye, azomethine
Dyes, triarylmethane dyes and phthalocyanine dyes
Fees are included. Emulsifying oil-soluble dyes in water to make them hydrophilic
It can also be added to the colloid layer. When the above dyes are used, the long-wavelength photosensitive
Dyes that have an absorption that causes the spectral sensitivity of the layers to overlap
It is preferable to use it selectively. Using these dyes
The optical density of the photosensitive material (the logarithm of the reciprocal of transmitted light,
(Reflection density in the case of a carrier)
Adjustment can improve the sharpness of the image.
You. The above optical density is 680 nm or used for exposure
Measure at the laser wavelength. The present invention provides that at least two different
It can be applied to multilayer multicolor photographic materials having different spectral sensitivities.
Multi-layer natural color photographic materials are usually red-sensitive on a support
It has an emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer. This
The arrangement order of these layers is determined as needed. Preferred
Red layer, green layer and blue layer from the support side
Order, blue-sensitive layer, green-sensitive layer and red-sensitive layer in order or blue sensitivity,
The order is red sensitivity and green sensitivity. Also any same photosensitive
Is composed of two or more emulsion layers having different sensitivities.
Thus, the reaching sensitivity may be improved. Also, as a three-layer configuration
Further, the graininess may be improved. Also has the same photosensitivity
A non-photosensitive layer may exist between two or more emulsion layers.
No. One photosensitive emulsion layer contains different photosensitive milk.
An agent layer may be inserted. Of the high-sensitivity layer, especially the high-sensitivity blue-sensitive layer
A reflective layer may be provided below to improve the sensitivity. One reflective layer
Generally contains fine grain silver halide. Generally, red-sensitive emulsion
Cyan-forming coupler for layers and magenta for green-sensitive emulsion layers.
-Forming coupler and yellow formation in blue-sensitive emulsion layer
Each coupler is added. Possibly different unions
You may adopt a set. For example, combining infrared-sensitive layers
In addition, pseudo color photosensitive materials and semiconductor laser exposure
It may be a material. Various color couplers can be used in the photographic light-sensitive material.
Can be used. For color couplers,
It is described in various patent documents. These references are
Chi Disclosure, 176, 17643 (19
78), paragraphs VII-CG. Yellow
U.S. Pat. No. 3,933,501;
Nos. 40222620, 432,024 and 440
Nos. 1752, JP-B-58-10739,
British Patent Nos. 1425020 and 1476760
There is a description in the specification. As the magenta coupler, 5-pyrazolo
And pyrazoloazole compounds are preferably used.
Can be For a magenta coupler, see US Pat.
Nos. 1432, 3725067 and 4310619
No. 4351897, No. 4500630, No. 45
40654 and EP 73636,
Search Disclosure, No. 24220 (198
4), No. 24230 (1984), JP-A-60-33
Nos. 552 and 60-43659.
You. Cyan couplers include phenolic and naph
Toll compounds are preferably used. Cyan coupler
Are described in U.S. Pat. Nos. 2,369,929 and 27721.
No. 62, No. 2801171, No. 2895826, No.
No. 3446622, No. 3758, No. 309, No. 3772
No. 002, No. 4052212, No. 4146396,
No. 4228233, No. 4296200, No. 4333
No. 999, No. 4327173, No. 4334011,
Nos. 4427767 and 4451559, West German Patent 3
329729, EP 121365A and 1
No. 61626A is described in each specification. In order to correct unnecessary absorption of coloring dyes,
Lard couplers may be used. Colored coupler
About, Research Disclosure, 176,
No. 17643 (1978), section VII-G, U.S. Pat.
No. 004926, No. 4138258, No. 416667
No. 0 and British Patent 1146368
No. 57-39413. Moderate coloring dye
A coupler having an excellent diffusibility may be used. like that
U.S. Pat. No. 4,366,237 and British Patent
Patent No. 2125570, European Patent 96570 and West Germany
It is described in each specification of Japanese Patent No. 3234533. Also using polymerized dye-forming couplers
Can be For such couplers, see the United States
Patent Nos. 3451820, 4080211 and 436
No. 7282 and British Patent No.
There is a description. Residues that are photographically useful with coupling
A coupler that emits can also be used. Releases development inhibitor
DIR couplers are research disclosures
VII-F of 176, 17643 (1978)
And JP-A-57-151944.
Nos. 57-154234 and 60-18424
No. 8 and U.S. Pat. No. 4,248,962.
I'm hanging. Nucleator or development accelerator in image form during development
For couplers that emit
Nos. 0 and 2131188, JP-A-59-1984.
Nos. 157638 and 59-170840
There is a description. Further, competitive couplers, multi-equivalent couplers,
DIR redox compound or DIR coupler release
Pullers, couplers that release dyes that recolor after detachment, bleaching
Use accelerator releasing coupler or ligand releasing coupler
It may be. Regarding competing couplers, see US Pat.
No. 30427. Multi-equivalent coupler
Nos. 4,283,472 and 4,310,618.
And No. 4,338,393. D
IR redox compound or DIR coupler releasing cap
Are described in JP-A-50-24252 and 6
It is described in each of Japanese Patent Publication Nos. 0-185950. Recolor after leaving
For couplers which release dyes, see EP 173
No. 302A. Bleach accelerator releasing coupler
About Research Disclosure 1144
No. 9, 24241, JP-A-61-201247
Described in the report. US for ligand releasing couplers
It is described in Japanese Patent No. 4553477. The above-mentioned couplers are generally known oil droplets in water.
It can be introduced into the photosensitive material by a dispersion method. By oil-in-water dispersion method
Uses a high-boiling organic solvent. About high boiling organic solvents
Are described in US Pat. No. 2,322,027. Yes
The boiling point of the organic solvent is preferably 175 ° C or higher at normal pressure.
New As high boiling organic solvents, phthalates,
Phosphoric acid or phosphonic acid esters, benzoic acid esters
, Amides, alcohols, phenols, aliphatic
Carboxylic esters, aniline derivatives and hydrocarbons
Are used. Examples of phthalates include dibutyl phthalate.
Tallate, dicyclohexyl phthalate, di-2-ethyl
Lehexyl phthalate, decyl phthalate, bis (2,
4-di-t-amylphenyl) phthalate, bis (2,
4-di-t-amylphenyl) isophthalate and
(1,1-diethylpropyl) phthalate
You. Examples of esters of phosphoric or phosphonic acids include
Liphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, trisic
Rohexyl phosphate, tri-2-ethylhexylho
Sulfate, tridodecyl phosphate, tributoxy
Ethyl phosphate, trichloropropyl phosphate
And di-2-ethylhexyl phenyl phosphate
included. Examples of benzoic acid esters include 2-ethyl
Xyl benzoate, dodecyl benzoate and 2-
Ethyl hexyl-p-hydroxybenzoate
You. Examples of amides include N, N-diethyldodecaneamido
, N, N-diethyllauramide and N-tetra
Decylpyrrolidone. Examples of alcohols include
Sostearyl alcohol. Examples of phenols are
2,4-di-tert-amylphenol. Aliphatic mosquito
Examples of rubonic esters include bis (2-ethylhexyl)
Le) sebacate, dioctyl azelate, glycerol
Tributyrate, isostearyl lactate and tri
Octyl citrate is included. Examples of aniline derivatives
Is N, N-dibutyl-2-butoxy-5-tert-octane
It is tilaniline. Examples of hydrocarbons include paraffin
, Dodecylbenzene and diisopropylnaphthalene
Is included. Using an auxiliary solvent in addition to the high boiling organic solvent
You may. The boiling point of the auxiliary solvent should be 30 ° C or higher.
Preferably, it is in the range of 50 to 160 ° C.
preferable. Use organic solvent as auxiliary solvent
Is preferred. Examples of co-solvents include ethyl acetate, butyric acetate
, Ethyl propionate, methyl ethyl ketone, cyclo
Hexanone, 2-ethoxyethyl acetate and dime
Includes tilformamide. The coupler is exposed by a latex dispersion method.
It may be added to the material. About latex dispersion method,
U.S. Pat. No. 4,199,363, West German Patent 2541274
And in each specification of Japanese Patent No. 2541230. Cap
A color image preservability improving compound may be added together with the colorant. color
The image preservability improving compound is described in European Patent 277589.
It is described in the specification of A2. The color image preservability improving compound is
Pyrazoloazole couplers and pyrrolotriazole couplers
Particularly preferred is the combined use of The above compound is used in a color developing process.
Chemical bonding with the remaining aromatic amine developing agent after processing
To produce chemically inert and virtually colorless compounds
I do. Alternatively, the above compound remains after color development processing.
Bonds to Oxidized Aromatic Amine Color Developing Agent
To produce chemically inert and virtually colorless compounds
I do. As a result, it remains in the membrane during storage after processing.
Between a developing color developing agent or its oxidized product and a coupler
To prevent the generation of stains due to the formation of colored pigments
Can be. It is possible to add a fungicide to photosensitive materials.
Wear. As fungicides, various fungi and bacteria are hydrophilic colloids
Prevents propagation in the layers and image degradation. Prevention
The fungicide is described in JP-A-63-271247.
There is a description. Each photographic functional layer is coated on a support. Yes
Both flexible and rigid supports are available. Yes
Is the flexible support made of plastic film, paper or cloth
It becomes. Is the rigid support glass, pottery or metal?
It becomes. Useful flexible supports are semi-synthetic or synthetic polymers
Plastic film and baryta layer
Is an α-olefin polymer (eg, polyethylene, polyp)
Propylene, ethylene / butene copolymer)
Minated paper. The plastic film is
Cellulose nitrate, cellulose acetate, cellulose acetate butyrate
, Polystyrene, polyvinyl chloride, polyethylene tele
Manufactured from phthalate or polycarbonate.
The support may be colored using a dye or a pigment. Shading
It may be black for the purpose. The surface of the support is generally
A primer coating is applied to improve adhesion with the true emulsion layer.
You. The support surface may be glowed before or after
Discharge, corona discharge, UV irradiation and flame treatment
Is also good. Coating of photographic emulsion layer and other hydrophilic colloid layers
Various known coating methods can be used for the cloth.
Examples of coating methods include dip coating, roller coating, and
The coating method includes extrusion coating and extrusion coating. Multiple layers
You may apply simultaneously. The multi-layer simultaneous coating method is
No.2681294, No.2761791 and No.3508
947 and 3526528.
You. The present invention is applicable to various color light-sensitive materials.
Can be Various photosensitive materials are for general use or
Color negative film for movie, slide or tele
Color reversal film, color paper,
Film and color reversal paper, color diffusion transfer
Photosensitive material and heat-developable color photosensitive material. Black and white
The present invention can be applied to photosensitive materials. The black and white photosensitive material is X
There is also a use as a line film. For black and white photosensitive material
The black image by mixing the three color couplers
Is also good. Also, black color coupler can be used
You. For research on mixing three-color couplers, see the Research Disc.
Roger, 17123 (1978).
U.S. Pat. No. 4,126,461 discloses a black color coupler.
And UK Patent No.
You. Made of squirrel film or scanner film
Plate film, direct / indirect medical or industrial X-ray
Film, negative black and white film for photography, black and white photographic paper, CO
For M or normal microfilm, silver salt diffusion transfer type
The present invention is applicable to optical materials and printout type photosensitive materials.
Can be used. The photographic light-sensitive material of the present invention is a color diffusion transfer.
It can also be applied to photography. Color diffusion transfer photography
The peel (peel apartment) type and peel-free type fill
There is a system unit configuration. For the release-free type,
Nos. 46-16356 and 48-33697,
Nos. 50-13040 and British Patent 133052
No. 4 describes this. In any of the above types,
Use a polymer acid layer protected by a neutralization timing layer.
It is preferred to use The polymer acid layer is allowed at the processing temperature.
It has a function to increase the width. Polymer acids are used for color expansion
It may be used by adding to any layer of the spread transfer photographic material.
Or as a developer component in a processing solution container.
You may. The light-sensitive material of the present invention employs various exposure means.
Can be. Radiation corresponding to the sensitivity wavelength of the photosensitive material
Any light source that emits a line,
Use as a source. Natural light (sunlight), incandescent lamp, halo
Genomic lamps, mercury lamps, fluorescent lamps and flash light sources
(Eg, strobe, metal-fired flash valve) is common
Used for Emit light in the wavelength range from ultraviolet to infrared
(Gas, dye solution or semiconductor)
Iodine and plasma light sources can also be used as recording light sources.
it can. Also, is the phosphor excited by an electron beam, etc.
Fluorescent screen (eg, CRT), liquid crystal (LCD),
Lanthanum-doped lead zirconate titanate (PLZ
T) using a micro-shutter array,
Or use an exposure means that combines a planar light source
Can be. If necessary, use a color filter for exposure.
The light distribution can be adjusted. The color developing solution used in the developing treatment is an aromatic developing solution.
Alkaline water containing primary amine color developing agent as a main component
It is preferably a solution. As color developing agents,
Minophenolic compound and p-phenylenediamine
Based compounds are available. p-phenylenediamine-based
Compounds are preferred. Examples of color developing agents include 3-meth
Tyl-4-amino-N, N-diethylaniline, 3-methyl
Tyl-4-amino-N-ethyl-N-β-hydroxy
Tylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-me
Tyl-4-amino-N-ethyl-N-β-methoxyethyl
Luaniline and their sulfates, hydrochlorides or p-
Toluenesulfonate is included. Diamines are free
Salt is generally more stable than salt, so salt
Used well. A color developing solution is generally used as a pH buffer (eg,
Alkali metal carbonates, borates, phosphates)
Image inhibitors or antifoggants (eg, bromide, iodide,
Benzimidazoles, benzothiazoles, mercap
Compound). If necessary, preservatives (eg, hydro
Xylamine, sulfurous acid), organic solvent (eg, triethanolamine)
Luamine, diethylene glycol), development accelerators (eg,
Benzyl alcohol, polyethylene glycol, quaternary alcohol
Ammonium salts, amines), dye-forming couplers,
Pullers, nucleating agents (eg, sodium boron hydride),
Auxiliary developing agents (eg, 1-phenyl-3-pyrazolidone),
Viscosity imparting agent, chelating agent (eg, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, phosphono
Carboxylic acid) and antioxidants (West German Patent 2622250)
(Described in the specification) may be added to the color developer. In the developing process of a reversal color photosensitive material,
Color development is performed after black and white development. Black and white developer
Contains a black-and-white developer. Examples of black-and-white developers include dihydro
Xybenzenes (eg, hydroquinone), 3-pyrazoli
Dones (eg, 1-phenyl-3-pyrazolidone) and
Aminophenols (eg, N-methyl-p-aminophen)
Nol) is included. Combines two or more black and white developers
They may be used together. The photographic emulsion layer after color development is usually subjected to a bleaching process.
Is done. The bleaching process may be performed simultaneously with the fixing process.
After the bleaching process, perform bleach-fixing to speed up processing.
You may employ the method of implementing. Polyvalent as bleach
Metal compounds, peracids, quinones and nitroso compounds
Is used. Polyvalent metals are generally iron (II), iron (III)
Cobalt (III), chromium (IV) or copper (II).
Examples of bleaches include ferricyanide, dichromate, iron
(III) or cobalt (III) organic complex, persulfuric acid,
Includes ganates and nitrosophenols. the above
Organic complex salts include aminopolycarboxylic acids (eg, ethylene dia
Mintetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotri
Acetic acid, 1,3-diamino-2-propanoltetraacetic acid)
And other organic acids (eg, citric, tartaric, malic)
It can be formed using. Ethylenediaminetetraacetic acid
Iron (III) salt, diethylenetriaminepentaacetic acid (III) and
Persulfates can be processed quickly and reduce environmental pollution
Therefore, it is preferably used. Iron ethylenediaminetetraacetate (I
II) Complex salts can be used in single-bath bleach-fix
Is also particularly useful. For bleaching solutions, bleach-fixing solutions and their prebaths
Can optionally add a bleaching accelerator.
Examples of bleach accelerators include mercapto groups or disulfides
Compounds having a group, thiazolidine derivatives, thiourea derivatives
Body, iodide, polyethylene oxides, polyamine
Includes compounds, iodide and bromide ions.
The compound having a mercapto group or a disulfide group,
It is preferably used because it has a large accelerating effect. Mercapto
For compounds having a thiol or disulfide group,
No. 3938858, West German Patent 1290812 and
And JP-A-2059988, JP-A-53-284.
No. 26, No. 53-32736, No. 53-57831
Nos. 37-418, 53-65832, 53
-72623, 53-95630, 53-95
No. 631, No. 53-104232, No. 53-1244
Publication Nos. 24 and 53-141623, Research
・ Disclosure, 17129 (1978)
There is. The thiazolidine derivative is disclosed in
It is described in JP-A-140129. Thiourea derivatives
For details, see JP-B-45-8506 and JP-A-52-20
Nos. 832 and 53-32735, U.S. Pat.
No. 3,706,561. About iodide
Japanese Patent No. 1127715, Japanese Patent Laid-Open No.
There is a description in JP-A-16235. Polyethylene oxide
Regarding the compounds, see German Patents 966410 and 27.
No. 48430. Polyamine compound
Is described in Japanese Patent Publication No. 45-8836.
You. Other bleaching accelerators are described in JP-A-49-42.
Nos. 434, 49-59644 and 53-94927
Nos. 54-35727, 55-26506 and
And JP-A-58-163940. These bleaching accelerators are added to the light-sensitive material.
You may. When bleach-fixing color photographic materials for photography
The use of a bleaching accelerator is particularly effective. Bleaching and fixing
Alternatively, a fixing agent is used in the fixing process. Examples of fixing agents
Is a thiosulfate, thiocyanate, thioether compound
Substances, thioureas and iodides (used in large amounts)
You. Thiosulfates are commonly used. Bleaching fixer and fixing
The liquid may include a preservative. Examples of preservatives include sulfite
Contains salts, bisulfite and carbonyl bisulfite adducts
It is. After bleach-fixing or fixing,
Usually, a washing process and a stabilizing process are performed. Washing treatment
Solution and stabilizing solution are used to prevent sedimentation and save water.
In this case, various additives may be used. For example, for processing solutions
Are water softeners, insecticides, anti-binders, metal salts (eg,
Nesium salt, aluminum salt, bismuth salt), surfactant
Agent or hardener can be added as needed
You. Water softeners are generally chelating agents and prevent precipitation
Used for Examples of hard softeners include inorganic phosphoric acid,
Minopolycarboxylic acid, organic aminopolyphosphonic acid and
Contains organic phosphoric acid. Various insecticides and anti-bacterial agents
Used to prevent the occurrence of ctereria, algae and mold
You. Surfactants are used to prevent drying load and unevenness.
Used. For other additives, see West, Ph.D.
Photographic Science and Engineering
Magazine (LE West, Photo. Sci. En)
g. ), Vol. 6, 344 (1965). Ki
The addition of a rating agent or an anti-binder is particularly effective. In the washing step, a plurality of tanks are generally used for countercurrent washing.
And save water. Multi-stage countercurrent stabilization process instead of washing process
May be performed. Multi-stage countercurrent stabilization process
The details are described in JP-A-57-8543. Many
The stepwise countercurrent stabilization process requires 2 to 9 countercurrent baths.
is there. In this stabilizing bath, in addition to the above additives,
Various compounds are added for the purpose of stabilizing an image. example
Buffer for adjusting the membrane pH (generally pH 3-9)
Additives and aldehydes (eg, formalin) into stabilizing bath
I do. Examples of the buffer include borate, metaborate,
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide
Thorium, aqueous ammonia, monocarboxylic acid, dicarboxylic
Contains acids, polycarboxylic acids and their combinations
You. If necessary, a chelating agent (eg, inorganic phosphorus
Acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphone
Acid, aminopolyphosphonic acid, phosphonocarboxylic acid), killing
Insecticide (eg, benzoisothiazolinone, irithiazolone,
4-thiazoline benzimidazole, halogenated pheno
, Sulfanilamide, benzotriazole)
Surfactants, optical brighteners and hardeners can be added to the stabilizing bath
Good. Two or more additives may be used in combination. A membrane pH adjuster may be added to the processing solution.
Ammonium is used as a membrane pH adjuster after such treatment.
The salt is preferably used. Examples of ammonium salts include:
Ammonium chloride, ammonium nitrate, ammonium sulfate
Ammonium phosphate, ammonium sulfite and titanium
Ammonium osulphate is included. With color sensitizer for photography
Is a process that is usually performed after fixing (washing-stable).
Replaced with the above stabilization process and washing process (water saving process)
Can also be obtained. Addition of formalin to this stabilizing bath
Is omitted when the magenta coupler has 2 equivalents.
Can be. The washing and stabilization processing time depends on the photosensitive material.
Determined by type and processing conditions. Processing time is generally
20 seconds to 10 minutes, 20 seconds to 5 minutes
More preferred. The silver halide color light-sensitive material can be easily processed.
Built-in color developer for simplicity and speed
Is also good. In that case, various precursors for color developing agents
Is preferred. Examples of precursors include in
Doaniline compounds, Schiff base compounds, aldols
Compound, metal complex salt, urethane compound and salt type compound
Is included. For indoaniline compounds, refer to the United States
It is described in Japanese Patent No. 3342592. Schiff base
For the type compound, see US Pat. No. 3,342,599.
, Research Disclosure, 14850 and
And No. 15159. About aldol compounds
In Research Disclosure, 13924
There is a description. For metal complex salts, see US Pat.
No. 92 is described. About urethane compounds
Are described in JP-A-53-135628. salt
For the type compound, JP-A-56-6235 and JP-A-56-6235
No. 16133, No. 56-54430, No. 56-59
No. 232, No. 56-67842, No. 56-81837
No. 56-83734, No. 56-83735, No.
Nos. 56-83736, 56-89735, 56-
No. 106241, No. 56-107236, No. 57-8
No. 3565 and No. 57-97531 are described.
is there. Silver halide color light-sensitive materials promote color development.
1-phenyl-3-pyrazolidones for the purpose of
May be stored. 1-phenyl-3-pyrazolidones
And JP-A-56-64339 and JP-A-57-1445.
No. 47, No. 57-111147, No. 58-50532
No., No. 58-50534, No. 58-50533, No.
58-50535, 58-50536 and 5
It is described in each of JP-A-8-115438. Various processing solutions are generally used at 10 to 50 ° C.
Used. 33-38 ° C. is the standard temperature. Standard temperature
Higher temperature to accelerate processing and reduce processing time
Good. Conversely, lower the temperature to improve the image quality and the stability of the processing solution.
Improvements may be achieved. To save silver on photosensitive materials,
Process using the intensification or hydrogen peroxide intensification
Is also good. Such processing is described in West German Patent 2226.
770 and US Pat. No. 3,674,499.
There is. A heater,
Temperature sensor, liquid level sensor, circulation pump, filter
-, Floating pigs or squeegees may be provided. In continuous processing, replenishers of each processing solution are used.
It may be used to prevent fluctuations in the liquid composition. Variation in composition
Prevention results in a certain finish. The amount of replenishment
Half or less than standard replenishment to reduce cost
Can also be reduced. When the photosensitive material is color paper
If this is the case, bleach-fix
Can be implemented. Photosensitive materials are color photographic materials for photography
If necessary, bleach-fix processing can be performed if necessary.
You. [0174] 【Example】 [Example 1] "Emulsion A: Preparation of Cubic Silver Emulsion" Sodium Chloride
Deionized gelatin is added to 845 ml of an aqueous solution containing 4.5 g.
25 g of the dissolved solution is kept at 50 ° C. while stirring.
140 ml of 0.21 M silver nitrate aqueous solution (solution 1) and 0.2 ml
Dub 140 ml of 1M sodium chloride aqueous solution (solution 2)
It was quantitatively added for 10 minutes by the Rujet method. After 10 minutes, 2.
320 ml of 2M silver nitrate aqueous solution (solution 3) and 2.2M chloride
Double-jet 320 ml of aqueous sodium solution (solution 4)
Further quantitative addition was carried out for 35 minutes by the same method. 5 minutes after completion of addition
Then, the temperature was lowered to 35 ° C, and soluble salts were
After removing, the temperature was raised again to 40 ° C and gelatin was added.
Dissolve and add sodium chloride and phenol
Then, the pH was adjusted to 6.5. The resulting particles are
Monodispersed silver chloride cube having a side length of 0.5 μm (coefficient of variation 15
%)Met. "Emulsions B-1 to B-3: (NH_Four )_Two [RhC
l_Five (H_Two O)]-doped silver chloride cubic emulsion
To the solution 4 of Emulsion A, each was added per mole of silver added.
1 × 10^-8, 1 × 10^-7And 1 × 10^-6Mole of (N
H_Four )_Two [RhCl_Five (H_Two O)], except that emulsion A
Emulsions B-1, B-2 and B-3 were prepared in the same manner as
Each was prepared. "Emulsion C-1 to 3: Emulsion C-1_Three [Cr (CN)
₆ Preparation of Cubic Silver Chloride Emulsion Doped with Emulsion "
1 × 10 5 per mol of silver added to liquid 4^-8,
1 × 10^-7And 1 × 10^-6Mole of K_Three [Cr (CN)
₆ ], Except that emulsions C-1 and C
-2 and C-3 were prepared, respectively. These emulsions A, B-1 to C-3 and C-1 to C-1
3, respectively, gelatin, dodecylbenzenesulfonic acid
Triacetyl cell with undercoat layer with addition of sodium
Gelatin, polymethylmeta on a roast film support
Acrylate particles, 2,4-dichloro-6-hydroxy-
Extruded with a protective layer containing sodium s-triazine salt
Silver amount 2g / m^Two And apply sample 1
7 were obtained. These samples were subjected to sensitometric exposure.
(10 seconds) through an optical wedge,
After developing with AA-1 * developer for 5 minutes at 20 ° C,
After stopping, fixing, washing with water and drying, the optical density was measured. [0179] ────────────────────────────────────   MAA-1 * developer ────────────────────────────────────     2.5g methol     L-ascorbic acid 10.0g     Nabox 35.0g     0.58 g of NaCl     1 liter with water ──────────────────────────────────── The sample was evaluated as follows. Fog
Was determined from the minimum optical density of the sample. Sensitivity is fog +
Expressed as the reciprocal of the exposure required to obtain an optical density of 0.5
The value for sample 1 was expressed as a relative value with the value being 100.
The gradation represents the slope of the linear portion of the characteristic curve.
It is key. The foot density is 0.8 of the exposure amount that gives the above sensitivity.
The minimum optical density from the optical density when a double exposure is given
Indicates the optical density that was subtracted.The lower the value, the more the characteristic curve
Indicates that The results are shown in Table 1. The first
The amount of dopant in the table is 1 mole of silver halide.
Per mole. [0181] [Table 1]                                 Table 1 ────────────────────────────────────   SampleDopant  Fog Sensitivity Gradation Foot density   No.Compound addition amount ────────────────────────────────────     1 None 0.06 100 2.6 0.32     2 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-8  0.05 56 1.0 0.33     3 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-7  0.05 39 3.2 0.27     4 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-6  0.05 5 4.1 0.21     5K_Three[Cr (CN)₆] 1 × 10^-8  0.05 74 2.3 0.32     6 K_Three[Cr (CN)₆] 1 × 10^-7  0.05 47 2.6 0.28     7 K_Three[Cr (CN)₆] 1 × 10^-6  0.05 10 5.7 0.07 ──────────────────────────────────── Example 2 Emulsion A prepared in Example 1
1 mol of silver was applied to B-2, B-3, C-2 and C-3.
1 × 10^-2Mole silver bromide fine grain emulsion, 2.5 × 10^-6
Molar sodium thiosulfate and 3 × 10^-7Molar chloride
Optimum chemical sensitization at 60 ° C by adding gold acid respectively
Was. Then, apply the same method as in Example 1
8 to 12 were obtained. These samples were the same as in Example 1.
It was evaluated as follows. The results are shown in Table 2. [0183] [Table 2]                                 Table 2 ────────────────────────────────────   SampleDopant  Fog Sensitivity Gradation Foot density   No.Compound addition amount ────────────────────────────────────     8 None 0.10 100 2.2 0.36     9 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-7  0.08 40 2.6 0.32   10 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-6  0.09 5 3.7 0.23   11 K_Three[Cr (CN)₆] 1 × 10^-7  0.07 64 4.0 0.25   12K_Three[Cr (CN)₆] 1 × 10^-6  0.05 9 6.4 0.15 ──────────────────────────────────── [Example 3] Milk prepared in Example 1
Ingredients A, B-3 and C-3 respectively
The ring compound (III-2-2) was added in an amount of 5 × 10^-3
After adding mol, apply in the same manner as above and apply
13-15 were obtained. Emulsions A, B-3, and C-3
Each of the tetrazaindene compound (IV-1) is 1 mol of silver
5 × 10 per^-3After the molar addition, use the same method as above.
It applied and the application samples 16-18 were obtained, respectively. these
The sample was evaluated as in Example 1. In addition, the maximum
Investigate high optical density (Dmax) and storage stability (ΔlogE)
Was. ΔlogE was measured after heating at 50 ° C for 3 days after application.
The difference between the sensitivity of the sample and the sample
I forgot. The results are shown in Table 3. In Table 3,
The results of Coated Samples 1, 4 and 7 are also reproduced for reference
You. [0185] [Table 3]                                 Table 3 ──────────────────────────────────── Sample Dopant Additive Fog Sensitivity Gradation Toe density Dmax ΔlogE ────────────────────────────────────   1 None None 0.06 100 2.6 0.32 1.85 +0.94   4 Rh None 0.05 5 4.1 0.21 1.35 +0.44   7 Cr None 0.05 10 5.7 0.07 1.40 +0.25 13 None III 0.05 115 2.8 0.27 1.98 +0.47 14 Rh III 0.05 8 4.4 0.20 2.10 +0.28 15 Cr III 0.05 11 5.9 0.06 2.12 +0.12 16 None IV 0.05 113 2.7 0.32 1.99 +0.42 17 Rh IV 0.05 7 4.3 0.21 2.08 +0.33 18 Cr IV 0.05 11 5.8 0.06 2.11 +0.14 ──────────────────────────────────── (Note) Rh: (NH_Four)_Two[RhCl_Five(H_TwoO)] at 1 × 10^-6Mole
use Cr: K_Three[Cr (CN)₆] To 1 × 10^-6Mole use III: Mercaptoheterocyclic compound III-2-2 per mole of silver
5 × 10^-3Mole use IV: 5 of tetrazaindene compound IV-1 per mole of silver
× 10^-3Mole use [Example 4] Milk prepared in Example 1
Agents A, B-3 and C-3 contained 1 × 10
^-2Mole silver bromide fine grain emulsion, 2.5 × 10^-6Mole thio
Sodium sulfate and 3 × 10^-7Moles of chloroauric acid
Each was added and optimally chemically sensitized at 60 ° C. afterwards,
Mercaptoheterocyclic compound (III-2-2) was converted to 1 mole of silver
5 × 10^-3After molar addition, apply in the same manner as above.
Cloth was applied to obtain coating samples 19 to 21, respectively. Also the same
Emulsions A, B-3 and C-3 after chemical sensitization
Compound (IV-1) in an amount of 5 × 10^-3Mo
After the addition, the sample was coated in the same manner as above,
2 to 24 were obtained respectively. These samples were the same as in Example 1.
It was evaluated as follows. Furthermore, the maximum optical density (Dmax) of each sample
And the storage stability (ΔlogE) was examined. ΔlogE is applied
After heating for 3 days at 50 ° C, the sensitivity of the sample
The difference from the sensitivity of the subsequent sample is represented by the amount of exposure.
The results are shown in Table 4. In Table 4, coating samples 8, 10 and
And the results of 12 are also reproduced for reference. [0187] [Table 4]                                 Table 4 ──────────────────────────────────── Sample Dopant Additive Fog Sensitivity Gradation Toe density Dmax ΔlogE ────────────────────────────────────   8 None None 0.10 100 2.2 0.36 1.85 +0.34 10 Rh None 0.09 5 3.7 0.23 1.65 +0.24 12 Cr None 0.05 9 6.4 0.15 1.60 +0.15 19 None III 0.08 108 2.5 0.42 1.88 +0.23 20 Rh III 0.07 7 4.6 0.22 2.12 +0.18 21 Cr III 0.07 10 6.7 0.13 2.14 +0.09 22 None IV 0.08 109 2.7 0.44 1.89 +0.22 23 Rh IV 0.07 9 4.5 0.23 2.10 +0.18 24 Cr IV 0.06 11 6.6 0.12 2.12 +0.08 ──────────────────────────────────── (Note) Rh: (NH_Four)_Two[RhCl_Five(H_TwoO)] at 1 × 10^-6Mole
use Cr: K_Three[Cr (CN)₆] To 1 × 10^-6Mole use III: Mercaptoheterocyclic compound III-2-2 per mole of silver
5 × 10^-3Mole use IV: 5 of tetrazaindene compound IV-1 per mole of silver
× 10^-3Mole use [Embodiment 5] "Preparation of 99% silver chloride emulsion sample" Same as emulsion A in Example 1.
After preparing the emulsion in the same manner, 1 ×
10^-2Mole silver bromide fine particles, sodium thiosulfate and
Optimum chemical sensitization at 60 ° C by adding chloroauric acid respectively
did. Then, the tetrazaindene compound was obtained in the same manner as in Example 3.
Compound (IV-1) was added before coating. Same as Example 1
Coating was performed in the same manner. The coating pH can be adjusted by adding sulfuric acid and
PH by adding water and sodium hydroxide
And measured according to the method described herein. This
At the time, according to Table 5, (NH_Four )_Two [RhCl_Five
(H_Two O)] and K_Three [Cr (CN)₆ ] Is 1 mole of silver
1 × 10 per^-6Moles to solution 4 of emulsion A and add
And 1 × 10 per mole of silver^-6Mole of K_Two
[IrCl₆ ] And 1.times.10@-5 mol of K_Four [Fe (C
N)₆ ] To Solution 4 of Emulsion A, and
The coating samples 25 to 30 were obtained. These samples were exposed to light for sensitometry.
(10 seconds) through an optical wedge,
After developing with AA-1 * developer for 5 minutes at 20 ° C,
After stopping, fixing, washing with water and drying, the optical density was measured.
The sensitivity is expressed as a relative value with the value of sample 25 being 100.
Other than the above, the fog, gradation, foot density, Dmax
And ΔlogE were examined, respectively. Fog is the
Determined at minimum optical density. "Preparation of 50% silver chloride emulsion sample"
Aqueous solution containing 2.3 g of lithium and 4.6 g of potassium bromide
To 845 ml of the solution, 25 g of deionized gelatin was added and dissolved.
Keep the solution at 70 ° C. and stir with 0.18 M aqueous silver nitrate.
140 ml of solution (solution 5) and 0.10 M sodium chloride
Solution and 0.10M potassium bromide mixed aqueous solution (Solution 6)
140 ml was added by the double jet method for 10 minutes.
Was. After 10 minutes, 320 M aqueous solution of silver nitrate (solution 7) 320
ml and 2.2 M aqueous sodium chloride solution (solution 8) 320
ml for a further 70 minutes by the double jet method.
Was. 5 minutes after completion of addition, the temperature was lowered to 35 ° C, and normal precipitation was performed.
After removing soluble salts by the method, the temperature was raised to 40 ° C again
And add gelatin to dissolve, add sodium chloride
And potassium bromide and phenol to pH 6.5
It was adjusted to become. The obtained particles have a side length of 0.5 μm.
It was a monodispersed silver chlorobromide cube (coefficient of variation 17%). This
Sodium thiosulfate, chloroauric acid and
Add potassium thiocyanide and add at 60 ° C
Appropriate chemical sensitization. Thereafter, tetraza was prepared in the same manner as in Example 3.
The indene compound (IV-1) was added before coating. It
The coating was performed in the same manner as in Example 1. The coating pH is also
The adjustment was made as described above. At this time, the emulsion before chemical sensitization was
According to Table 5, (NH_Four )_Two [RhCl_Five H_Two
O)] and K_Three [Cr (CN)₆ ] Per mole of silver
1 × 10^-6Moles to solution 8 and make additions,
1 × 10 per mole of silver^-6Mole of K_Two [IrCl₆ ]
And 1 × 10^-FiveMole of K_Four [Fe (CN)₆ ] To solution 8
In addition to the above, coating samples 31 to 3
6 was obtained. These samples were exposed to light for sensitometry.
(10 seconds) through an optical wedge,
After developing with AA-1 developer at 20 ° C. for 10 minutes,
Stop, fix, wash, dry and measure optical density.
Was. Regarding sensitivity, relative value with the value of sample 31 being 100
Other than the above, fog, gradation, foot density,
Dmax and Δlog E were examined, respectively. [0192] ────────────────────────────────────   MAA-1 developer ────────────────────────────────────     2.5g methol     L-ascorbic acid 10.0g     Nabox 35.0g     1.0 g of KBr     1 liter with water ──────────────────────────────────── "100% silver bromide (0% silver chloride) emulsion sample
Preparation of 36 g of deionized gelatin in 870 ml of water
0.25 g of potassium bromide was added and dissolved. 75 ° C
0.088 with stirring in this maintained gelatin aqueous solution.
36 ml of M silver nitrate aqueous solution (solution 9) and 0.088 M bromide
Double 36 ml of potassium aqueous solution (solution 10) for 10 minutes
A fixed amount was added by a jet method, and then each of Solution 9 and Solution 10 was added.
176 ml each were added by the double jet method in 7 minutes.
Thereafter, 898 m of a 0.82 M silver nitrate aqueous solution (solution 11)
First, accelerate the flow rate from a flow rate of 0.53 ml / min.
For 95 minutes while simultaneously adding 0.90 M potassium bromide.
Solution (Solution 12) at a silver potential of +120 mV (vs.
(Melted electrode).
Five minutes after completion of the addition, the temperature was lowered to 35 ° C.
After removing the soluble salts, the temperature was raised again to 40 ° C.
g gelatin and then dissolved.
Enol was added and adjusted to pH 6.5.
The resulting particles are monodispersed silver bromide cubes with a side length of 0.5 μm.
(Variation coefficient 13%). Sodium thiosulfate, salt
Fluorinated acid and potassium thiocyanate
Optimal chemical sensitization at 60 ° C. After that, the same as in Example 3
Add tetrazaindene compound (IV-1) before coating
did. It was applied in the same manner as in Example 1. Suffered
The membrane pH was also adjusted as described above. At this time, chemical sensitization
According to Table 5, (NH_Four )_Two [RhCl
_Five(H_Two O)] and K_Three [Cr (CN)₆ ] 1 silver
1 × 10 -5 or 1 × 10 per le^-6Moles into solution 12
In addition, additions were made. Sensitometry is used for these samples.
Exposure (10 seconds) through an optical wedge,
After developing at 20 ° C for 10 minutes with one MAA-1 developer
Stop, fix, wash, dry and measure optical density using standard methods
did. Regarding the sensitivity, relative to the value of sample 37 as 100
Fog, tone, and foot density
The degree, Dmax and ΔlogE were determined respectively. The result
The results are shown in Table 5. [0195] [Table 5]                                 Table 5 ──────────────────────────────────── Sample Chloride dopant film Fog Sensitivity Gradation Toe density Dmax ΔlogE       Silver I II pH ──────────────────────────────────── 25 99 Rh None 5.7 0.07 100 4.5 0.23 2.10 +0.18 26 99 Rh Ir 5.8 0.07 103 4.7 0.21 2.12 +0.15 2799 Rh Fe 5.9 0.06 101 4.8 0.22 2.11 +0.17 29.99 No Cr 5.8 0.06 125 6.6 0.12 2.12 +0.08 2999 Cr Ir 5.7 0.07 128 6.8 0.10 2.13 +0.06 30 99 Cr Fe 5.9 0.06 124 6.7 0.11 2.13 +0.07 31 50 Rh None 5.6 0.06 100 4.0 0.26 1.99 +0.15 32 50 Rh Ir 5.8 0.08 105 4.2 0.25 2.02 +0.12 3350 Rh Fe 5.7 0.07 102 4.3 0.25 2.05 +0.13 34 50 Cr None 5.7 0.07 119 4.3 0.19 2.00 +0.12 35 50 Cr Ir 5.8 0.07 122 4.5 0.17 2.07 +0.10 36 50 Cr Fe 5.9 0.08 120 4.6 0.18 2.06 +0.12 370 0 Rh * None 5.8 0.07 100 3.0 0.28 2.01 +0.30 380 Rh None 5.7 0.08 13 3.9 0.25 1.95 +0.30 390 Cr * None 5.9 0.08 180 2.6 0.29 2.00 +0.31 400 Cr None 5.8 0.07 60 3.0 0.28 1.97 +0.30 ──────────────────────────────────── (Note) Rh: (NH_Four)_Two[RhCl_Five(H_TwoO)] at 1 × 10^-6Mole
use Rh *: (NH_Four)_Two[RhCl_Five(H_TwoO)] at 1 × 10^-7Mole
use Cr: K_Three[Cr (CN)₆] To 1 × 10^-6Mole use Cr *: K_Three[Cr (CN)₆] To 1 × 10^-7Mole use Ir: K_Two[IrCl₆] To 1 × 10^-6Mole use Fe: K_Four[Fe (CN)₆] To 1 × 10^-6Mole use [Embodiment 6] "Preparation of Emulsion D" An aqueous gelatin solution (teto
Razaindene compound (IV-1) was added in an amount of 5 × 1 per mole of silver.
0^-3Mole) of silver nitrate aqueous solution and 4 moles per mole of silver.
10-5 moles of (NH_Four )_Two [RhCl_Five (H_Two O)]
Sodium chloride aqueous solution containing
By controlling the silver potential to 95 mV during
Thus, a core particle of 0.12 μm was prepared. Then,
1.2 × 10 per silver salt aqueous solution and silver mole^-FourMole of (N
H_Four )_Two [RhCl_Five (H_Two O)] containing sodium chloride
Aqueous solution at the same time for 14 minutes, during which the potential was 95
Average particle size by controlling to mV
Silver chloride cubic grains of 0.15 μm were prepared. "Preparation of Emulsion E" (NH_Four )_Two [RhCl_Five (H_Two O)] (core
Part and shell part) in a ratio of 6.5 × 10^-Five
Except for molesEmulsion DIt was prepared in the same manner as described above. "Preparation of emulsion F" (NH_Four )_Two [RhCl_Five (H_Two O)]
, K_Three [Cr (CN)₆ Except thatEmulsion DWhen
Prepared in a similar manner. "Preparation of Emulsion G" (NH_Four )_Two [RhCl_Five (H_Two O)]
, K_Three [Cr (CN)₆ Except thatEmulsion EWhen
Prepared in a similar manner. "Preparation of Emulsion H" (NH_Four )_Two [RhCl_Five (H_Two O)]
Instead of using an aqueous solution of lithium, 8 × 1
0^-FiveMole of K_Three [Cr (CN)₆ ] Containing sodium chloride
Aqueous solution in the core, 2.4 × 10^-FourMo
Le K_Three [Cr (CN)₆ Aqueous solution of sodium chloride
Except that the liquid is used for the shell to form particlesEmulsion Dthe same as
Prepared by the method described in "Preparation of Emulsion I" (NH_Four )_Two [RhCl_Five (H_Two O)]
Instead of using an aqueous solution of lithium, 1.3 moles per mole of silver
× 10^-FourMole of K_Three [Cr (CN)₆ ] Containing sodium chloride
Except using an aqueous solution of lithiumEmulsion EPrepared in the same way as
I got it. (Preparation of coating sample) First photosensitive emulsion layer The following additives were added to Emulsion D to give a silver content of 1.7 g / m @ 2.
(Gelatin 0.9 g / m2^Two ). [0203] ────────────────────────────────────   First photosensitive emulsion layer ────────────────────────────────────   0.6 g / m of polyethyl acrylate latex (average particle size: 0.05 μm)^Two   4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene                                                         30mg / m^Two     Compound A 40mg / m^Two   Compound B 10 mg / m^Two   Hardener (Compound C) 98mg / m^Two   Compound D 53mg / m^Two       ──────────────────────────────────── [0204] Embedded image [0205] Embedded image [0206] Embedded image[0207] Embedded image The second photosensitive emulsion layer On the first photosensitive emulsion layer, the compound D
The same as the first photosensitive emulsion layer except that
1.3g / m of silver^Two And gelatin 0.7g / m^Two When
A second photosensitive emulsion layer was coated. Protective lower layer On top of this, a protective lower layer having the following composition was coated with 0.55 g / m 2 of gelatin.
^Two It applied so that it might become. [0209] ────────────────────────────────────   Protective lower layer ────────────────────────────────────   1-hydroxy-2-benzaldoxime 15 mg / m^Two   Compound E 80mg / m^Two   Compound F 10mg / m^Two   0.28 g / m of polyethyl acrylate latex (average particle size 0.05 μm)^Two ──────────────────────────────────── [0210] Embedded image [0211] Embedded image [0212] Protective upper layer On top of this, a protective upper layer having the following composition was gelatin 0.95
g / m^Two It applied so that it might become. [0213] ────────────────────────────────────   Protective lower layer ────────────────────────────────────   Amorphous matting agent (silicon dioxide, average particle size 3.0 μm) 30 mg / m^Two   Spherical matting agent (PMMA, average particle size 2.7 μm) 30 mg / m^Two   Liquid paraffin gelatin dispersion 50mg / m^Two   N-perfluorooctanesulfonyl-N-propylglycine potassium                                                           5mg / m^Two   Sodium dodecylbenzenesulfonate 10mg / m^Two   Water-soluble dye (Compound G) 45mg / m^Two       ──────────────────────────────────── [0214] Embedded image[0215] Support Biaxially stretched polyethylene terephthalate as support
An undercoat layer having the following composition on both sides of the support (thickness: 100 μm)
What applied the 1st layer and the 2nd layer was used. Undercoat layer First layer Add 10% by weight of potassium hydroxide to the following ingredients, and add
The coating solution adjusted to 6 was dried at 180 ° C. for 2 minutes,
Coating was performed so that the dry film thickness became 0.9 μm. [0217] ────────────────────────────────────   Undercoat layer 1st layer ────────────────────────────────────   The following core-shell type vinylidene chloride copolymer: 15 g   0.25 g of 2,4-dichloro-6-hydroxy-s-triazine   Polystyrene fine particles (average particle size: 3 μm) 0.05 g   Compound H 0.20 g   Colloidal silica (Sonotex ZL: particle size 70-100 μm, Nissan Chemical ( 0.12g   Add water and add 100g ──────────────────────────────────── [0218] Embedded image [0219] Embedded image Undercoat Layer Second Layer The following coating solution was dried at 170 ° C for 2 minutes,
It was applied to a thickness of 0.1 μm. [0221] ────────────────────────────────────   Undercoat layer 2nd layer ────────────────────────────────────   1g gelatin   Methyl cellulose 0.05g   Compound I 0.02 g   C₁₂H_{twenty five}O (CH_Two CH_Two O)_TenH 0.03g   Compound J 3.5 × 10^-3g   Acetic acid 0.2g   Add water and add 100g ──────────────────────────────────── [0222] Embedded image[0223] Embedded image Then, on the opposite surface of the support,
The conductive layer and the back layer were simultaneously coated. [0225] ────────────────────────────────────   Conductive layer ────────────────────────────────────   SnO_Two / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m^Two   Gelatin (Ca2 + content 3000ppm) 77mg / m^Two   Compound K 7mg / m^Two   Sodium dodecylbenzenesulfonate 10mg / m^Two   Dihexyl-α-sulfosuccinate sodium 40 mg / m^Two   Sodium polystyrene sulfonate 9mg / m^Two ──────────────────────────────────── [0226] Embedded image [0227] ────────────────────────────────────   Back layer ────────────────────────────────────   Gelatin (Ca²⁺(Content: 30 ppm) 2.82 g / m^Two   Polymethyl methacrylate fine particles (average particle size: 3.4 μm) 54 mg / m^Two   Compound K 3mg / m^Two   Compound L 40mg / m^Two   Compound M 40 mg / m^Two   Compound N 80mg / m^Two   Compound O 120mg / m^Two   Sodium dodecylbenzenesulfonate 75mg / m^Two   Dihexyl-α-sulfosuccinate sodium 20 mg / m^Two   Compound P 5mg / m^Two   Sodium sulfate 50mg / m^Two   Sodium acetate 85mg / m^Two   1,2-bis (vinylsulfonylacetamido) ethane 150mg / m^Two ──────────────────────────────────── [0228] Embedded image[0229] Embedded image [0230] Embedded image [0231] Embedded image [0232] Embedded image A coating sample 41 was prepared by the above method.
Emulsion F was used instead of Emulsion D in the first photosensitive layer,
Same as sample 1 except that emulsion G was used instead of emulsion E in the layer
Application sample 42 was obtained by the following method. In addition, the first photosensitive layer contains milk.
Emulsion H in place of Agent D and Emulsion E in the second photosensitive layer
Except that emulsion I was used.
43 was obtained. The evaluation was performed by the following test methods. Photo features
The character is a light room printer P-6 manufactured by Dainippon Screen Co., Ltd.
After exposure through an optical wedge at 27FM, a developer with the following formulation
FG-680A automatic processor (Fuji Photo Film Co., Ltd.)
The results are obtained by performing a treatment at 38 ° C. for 20 seconds using the method described above. Set
The coating was carried out by a usual method (fixing solution: GR-F1). Real
The technique sensitivity is based on an original consisting of halftone dots and thin lines (Japanese Patent Laid-Open No. 58-19 / 1983).
50% with the above printer using Fig. 1 of No. 0943)
The halftone dot area of each sample site should be 50%
With the relative value of the reciprocal of the appropriate exposure amount, the value of sample 41
Was. Practical skill Dmax is the maximum black when the proper exposure amount is given.
Is the chemical concentration. The processing is the same as above. The gradation is a characteristic
The value of sample 41 was set to 100 as the relative value of the slope of the curve. Big
The harder the tone becomes. The processing is the same as above. [0235] The test for the quality of the extracted characters is performed by using halftone dots and thin lines.
Original (Fig. 1 of JP-A-58-190943)
And exposed with the above printer. Processing is for photographic properties
Is the same as Here, the character image quality 5 is the same as that in FIG.
50% of the halftone dot area on the photosensitive material
30 μm width when properly exposed to have 0% halftone dot area
Very good character image with good image quality to reproduce characters
It refers to quality. On the other hand, it is the same
Only characters with a width of 150 μm or more are reproduced when exposed
Good image quality that can not be done
Good, rank between 4 and 2 in sensory evaluation between 5 and 1
Was. 3 or more is a practical level. Next, the composition of the developer is shown below. ────────────────────────────────────   Developer ────────────────────────────────────   Potassium hydroxide 35.0 g   2.0 g of diethylenetriaminepentaacetic acid   Potassium carbonate 12.0g   Sodium metabisulfite 40.0g   3.0 g of potassium bromide   Hydroquinone 25.0g   0.08 g of 5-methylbenzotriazole   4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone                                                           0.45g   2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quina Zolinone 0.04g   2-mercaptobenzimidazole-5-sulfonic acid sodium salt                                                           0.15g   Sodium erythorbate 3.0g   1 liter with water   PH = 10.5 by adding potassium hydroxide ──────────────────────────────────── The above results are shown in Table 6. [0238] [Table 6]                                 Table 6 ────────────────────────────────────   Sample Dopant Sensitivity Dmax Tone Image quality without gradation   41 (NH_Four)_Two[RhCl_Five(H_TwoO)] 100 5.2 100 3   42K_Three[Cr (CN)₆] 115 5.4 91 4   43K_Three[Cr (CN)₆] * 99 5.3 105 5 ──────────────────────────────────── (Note) K_Three[Cr (CN)₆] *: Used in relatively large quantities [0239]Example 7] (Preparation of emulsion J) Add 32 g of lime-processed gelatin to 800 ml of distilled water,
After dissolving at 40 ° C, add 5.76 g of sodium chloride
Then, the temperature was increased to 55 ° C. N, N'-
Dimethyl imidazolidine-2-thione (1% aqueous solution)
1.0 cc was added. Subsequently, 100 g of silver nitrate was added to distilled water 4.
The solution dissolved in 00 ml and 34.4 g of sodium chloride were steamed.
The solution dissolved in 400 ml of distilled water is
The mixture was added to and mixed with the above solution over 35 minutes. Next, silver nitrate 5
A solution prepared by dissolving 9.2 g in 200 ml of distilled water and sodium chloride
And a solution obtained by dissolving 17.1 g of Pt in 200 ml of distilled water.
The mixture was added and mixed over 18 minutes while maintaining the temperature at 55 ° C. 40
After cooling to ℃, the following red-sensitive sensitizing dyes are halogenated
4 × 10 per mole of silver^-FiveMoles, and then add silver nitrate 0.
8 g dissolved in 100 ml distilled water and potassium bromide
A solution prepared by dissolving 0.56 g in 100 ml of distilled water was added to 40
The mixture was added and mixed over 10 minutes while maintaining the temperature. Desalination and
After washing with water and adding 90 g of lime-treated gelatin,
PAg with sodium chloride and sodium hydroxide
The pH was adjusted to 7.3 and the pH to 6.2. Heated to 50 ° C
Thereafter, gold-sulfur sensitization was optimally performed. Obtained in this way
Silver chlorobromide emulsion (containing 0.5 mol% of silver bromide)
did. (Preparation of Emulsion K)
1 × 10 per mole of silver chlorobromide^-8Mole of K_Three [RhC
l₆ ] To the second addition of sodium chloride solution
A silver chlorobromide emulsion was prepared in the same manner as described above. Emulsion K refers to sodium chloride added second time
The type and amount of metal complex added to the solution
Except for the changes, the silver chlorobromide emulsions L to S were prepared in the same manner.
Made. The emulsions J to S thus prepared were prepared as follows.
The particle shape, particle size,
And particle size distribution were determined. Particle size is particle projection
Expressed as the average of the diameter of the circle equivalent to the area, the particle size
Is the value obtained by dividing the standard deviation of the particle size by the average particle size.
Was used. Emulsions J to S all had a grain size of 0.4
5 μm, cubic particles having a particle size distribution of 0.09
Was. (Preparation of photosensitive material 101) Polyethylene
Corona discharge treatment is applied to the surface of the paper support laminated on both sides.
Contains sodium dodecylbenzenesulfonate
Provide gelatin undercoat layer and apply various photographic constituent layers
Then, a multi-layer color photographic paper (101) having a layer structure shown below is obtained.
Produced. Preparation of third layer coating solution Magenta coupler (ExM) 40.0g, UV absorber
(UV-2) 40.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-5) 25.0 g, color image
2.5 g of stabilizer (Cpd-6), color image stabilizer (Cpd-
7) 20.0 g, 2.5 g of color image stabilizer (Cpd-8),
5.0 g of a color image stabilizer (Cpd-10) was added to a solvent (Sol).
v-3) 32.5 g, solvent (Solv-4) 97.5
g, solvent (Solv-6) 65.0 g and ethyl acetate 1
Dissolve in 10 ml and add 10% dodecylbenzene
7% gelatin aqueous solution containing sodium sulfonate 90ml
Emulsified dispersion A was prepared by emulsifying and dispersing in 1500 g of liquid.
Was. On the other hand, a silver chlorobromide emulsion (cubic, average grain size of 0. 1).
55μm large size emulsion and 0.39μm small size emulsion
1: 3 mixture (silver molar ratio). Variation of particle size distribution
The numbers are 0.08 and 0.06, respectively, for each size emulsion
0.8 mol% of silver bromide on the surface of a grain based on silver chloride
In some parts, it was contained locally. 1 mole of silver in the grain and the localized phase of silver bromide
Potassium hexachloroiridate (IV)
0.1 mg and potassium ferrocyanide
In total, 1.0 mg was contained. ) Was prepared. This milk
The agents are green sensitizing dyes D, E and F shown below in large size.
The emulsions were 3.0.times.10@-4 and 4.0, respectively, per mole of silver.
× 10^-FiveMol, 2.0 × 10 -4, and the small-sized emulsion
3.6 × 10 -4 and 7.0 × 10 4 per mole of silver, respectively.
^-FiveMol, 2.8 × 10 -4, then sulfur sensitizer and gold
Optimizing chemical sensitization by adding a sensitizer in the presence of nucleic acid degradation products
Done. The emulsified dispersion A and the silver chlorobromide emulsion are combined with each other.
Mix and dissolve, and apply the third layer coating solution to the composition shown below.
Was prepared. The other coating solutions for the first to seventh layers are also the third layer.
It was prepared in the same manner as the coating solution. Gelatin hardener for each layer
As 1-oxy-3,5-dichloro-s-tria
Gin sodium salt was used. Further, Cpd-12 is added to each layer.
And Cpd-13 in a total amount of 25.0 mg / m 2 respectively.^TwoAnd 5
0.0mg / m^TwoWas added so that Each photosensitive emulsion layer
The following are the spectral sensitizing dyes for silver chlorobromide emulsions
Each was used. Blue-sensitive emulsion layer [0246] Embedded image [0247] Embedded image [0248] Embedded image (Large size emulsion per mole of silver halide
To 1.4 × 10^-FourMol, also small size milk
1.7 × 10^-FourMole used. ) Green-sensitive emulsion layer [0250] Embedded image [0251] Embedded image [0252] Embedded image(Sensitizing dye D was used per mole of silver halide,
3.0 × 10 for large size emulsions^-FourMole, small
3.6 × 10 for size emulsion^-FourMol, sensitizing dye
E is per mole of silver halide and per large emulsion
Is 4.0 × 10^-FiveFor mol and small size emulsions
Is 7.0 × 10^-FiveMole, sensitizing dye F is silver halide 1
Per mole, 2.0 × 10^-FourMo
2.8 × 10 for small size emulsions^-FourMole
Was added. ) Red-sensitive emulsion layer [0254] Embedded image (Sensitizing dye G was added per mole of silver halide,
4.0 × 10^-FiveMole was added. ) In addition, the following compounds were added to the red-sensitive silver halide emulsion
2.6 × 10 per mol of silver genide^-3Mole was added. [0256] Embedded image A blue-sensitive emulsion layer, a green-sensitive emulsion, a red-sensitive emulsion
1- (5-methylureidophenyl)
) -5-mercaptotetrazole with halogen
8.5 × 10 per mol of silver halide^-Four3.0 × 10^-3,
2.5 × 10^-FourMole was added. Blue sensitive emulsion layer and green
K for the emulsion layer_Three "Cr (CN)₆ ]
1 x 10 per mole of silver logenide^-Four, 2 × 10^-FourMoles
Added. In order to prevent irradiation, milk
Add the following dye to the agent layer
Was. Further, the coating pH was adjusted to 5.9. [0259] Embedded image [0260] Embedded image [0261] Embedded image(Layer Structure) The composition of each layer is shown below. Numbers
Is the coating amount (g / m^Two). However, silver halide emulsion
Represents a silver equivalent application amount. Support (A) The resin layer on the first layer contains a blue dye (ultra blue). [0264] First layer (blue-sensitive emulsion layer)   Silver chlorobromide emulsion (cubic, large size emulsion having an average grain size of 0.88 μm and 0.7 5: 5 mixture of 0 μm small size emulsions (silver molar ratio). Coefficient of variation of particle size distribution Are 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide is chlorided in each size emulsion. The silver was localized and contained on a part of the surface of the particle having the substrate. Silver in grain interior and silver bromide localized phase 0.1 mg of potassium hexachloroiridate (IV) per mole, And potassium ferrocyanide in a total amount of 1.0 mg) 0.27   Gelatin 1.22   Yellow coupler (ExY) 0.79   Color image stabilizer (Cpd-1) 0.08   Color image stabilizer (Cpd-2) 0.04   Color image stabilizer (Cpd-3) 0.08   Color image stabilizer (Cpd-5) 0.01   Solvent (Solv-1) 0.13   Solvent (Solv-5) 0.13 [0265] Second layer (color mixture prevention layer)   Gelatin 0.90   Color mixing inhibitor (Cpd-4) 0.08   Solvent (Solv-1) 0.10   Solvent (Solv-2) 0.15   Solvent (Solv-3) 0.25   Solvent (Solv-8) 0.03 [0266] Third layer (green-sensitive emulsion layer)   Silver chlorobromide emulsion (cubic, large size emulsion having an average grain size of 0.55 μm and 0.3 1: 3 mixture of 9 μm small size emulsions (silver molar ratio). Coefficient of variation of particle size distribution Are 0.08 and 0.06, respectively, and 0.8 mol% of silver bromide is chlorided in each size emulsion. The silver was localized and contained on a part of the surface of the particle having the substrate. Silver in grain interior and silver bromide localized phase 0.1 mg of potassium hexachloroiridate (IV) per mole, And potassium ferrocyanide in a total amount of 1.0 mg) 0.13   Gelatin 1.45   Magenta coupler (ExM) 0.16   UV absorber (UV-2) 0.16   Color image stabilizer (Cpd-2) 0.03   Color image stabilizer (Cpd-5) 0.10   Color image stabilizer (Cpd-6) 0.01   Color image stabilizer (Cpd-7) 0.08   Color image stabilizer (Cpd-8) 0.01   Color image stabilizer (Cpd-10) 0.02   Solvent (Solv-3) 0.13   Solvent (Solv-4) 0.39   Solvent (Solv-6) 0.26 [0267] 4th layer (color mixture prevention layer)   Gelatin 0.68   Color mixing inhibitor (Cpd-4) 0.06   Solvent (Solv-1) 0.07   Solvent (Solv-2) 0.11   Solvent (Solv-3) 0.18   Solvent (Solv-8) 0.02 [0268] Fifth layer (red-sensitive emulsion layer)   The silver chlorobromide emulsion A 0.18   Gelatin 0.80   Cyan coupler (ExC) 0.33   UV absorber (UV-2) 0.18   Color image stabilizer (Cpd-1) 0.33   Color image stabilizer (Cpd-2) 0.03   Color image stabilizer (Cpd-6) 0.01   Color image stabilizer (Cpd-8) 0.01   Color image stabilizer (Cpd-9) 0.02   Color image stabilizer (Cpd-10) 0.01   Solvent (Solv-1) 0.01   Solvent (Solv-7) 0.22 [0269] 6th layer (UV absorbing layer)   Gelatin 0.48   UV absorber (UV-1) 0.38   Color image stabilizer (Cpd-5) 0.01   Color image stabilizer (Cpd-7) 0.05   Solvent (Solv-9) 0.05 [0270] 7th layer (protective layer)   Gelatin 0.90   Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%)                                                           0.05   Liquid paraffin 0.02   Color image stabilizer (Cpd-11) 0.01 The compounds used are shown below. [0272] Embedded image[0273] Embedded image [0274] Embedded image [0275] Embedded image [0276] Embedded image [0277] Embedded image[0278] Embedded image [0279] Embedded image [0280] Embedded image [0281] Embedded image [0282] Embedded image [0283] Embedded image [0284] Embedded image [0285] Embedded image[0286] Embedded image [0287] Embedded image [0288] Embedded image [0289] Embedded image [0290] Embedded image[0291] Embedded image [0292] Embedded image [0293] Embedded image [0294] Embedded image [0295] Embedded image [0296] Embedded image [0297] Embedded image [0298] Embedded image A sample 101 was prepared as described above. Next
As shown in Table 7, the fourth layer (red-sensitive layer) of silver chlorobromide milk
Sample 1 was prepared in the same manner as Sample 101 except that the agent was changed.
Nos. 02 to 110 were produced. To examine the foot gradation of the sample thus obtained
Then, the sample is passed through an optical wedge and a red filter.
Give 1 second exposure and use the processing steps and processing solution shown below
To perform color development. Optical density of this processed sample
The degree was measured to obtain a characteristic curve. As an index of foot gradation,
Exposure amount and reflection density required to provide an emission density of 0.2.
Using the logarithmic difference ΔLogE of the exposure required to produce
Was. The smaller the value of ΔLogE, the more legs are cut off
It is a preferable gradation that can obtain a clear image with good quality
It indicates that. To investigate the safelight safety of a sample
The sample was a 20W bulb and a 103A made by Fuji Photo Film.
Safe consisting of two filters and one paraffin paper
Place the sample at a distance of 1 m from the light,
After a predetermined time exposure, the optical wedge and red filter
Exposure for 0.1 second, and the following processing steps
A color developing process was performed using a physical solution. This sailfly
And the treated sample irradiated with safe light
The optical density of the untreated sample was measured to obtain a characteristic curve.
Safelight safety indicators include safelight illumination.
Required to provide a reflection density of 0.3 for unirradiated samples
The exposure required for the reflection density to reach 0.4
The flight light irradiation time t was used. Safelight light irradiation
The shorter the time t is, the more the density changes due to safelight light irradiation.
And safe light safety.
And To examine the raw preservability of the sample,
After storing for 1 week in an atmosphere of 0 atm, the optical wedge and
Give a 0.1 second exposure through the red filter and
Performed color development using the processing steps and processing solutions shown.
Was. Samples stored for one week in this 50 atmosphere atmosphere
Measure the optical density of the processed sample
A sex curve was obtained. As an indicator of raw preservation,
And the exposure required to produce a reflection density of 1.0
Reflection density of a sample stored for one week under an atmosphere of 0 atm.
Using the logarithmic difference ΔLogE of the exposure amount required to produce 0
Was. When the value of ΔLogE is a positive value,
Indicates an increase in sensitivity, with negative values indicating
It shows that the sensitivity decreases more. The absolute value of ΔLogE is
A smaller value indicates better raw preservability. In order to examine the exposure humidity dependency of the sample,
The atmosphere is 25 ° C 40% RH and 25 ° C 85% RH
0.1 seconds through the optical wedge and red filter below
Gives exposure and develops color using the following processing steps and processing solutions
A development process was performed. This 25 ° C. 40% RH and 25%
Of processed samples exposed in an atmosphere of 85 ° C and 85% RH
The concentration was measured to obtain a characteristic curve. Exposure humidity dependency index and
Of the sample exposed at 25 ° C. and 40% RH.
Exposure and 25 ° C 85 required to produce a reflection density of 1.0
The reflection density of the sample exposed in an atmosphere of
The logarithmic difference ΔLogE of the amount of exposure required for cleaning was used.
When the value of ΔLogE is a positive value, the sensitivity in high humidity exposure
Increases, and a negative value indicates exposure under high humidity.
Indicates that the sensitivity decreases. Absolute value of ΔLogE is small
It shows that the exposure humidity dependency is excellent. [0304] ────────────────────────────────────   Processing process Temperature Time Replenishment amount * Tank capacity ────────────────────────────────────   Color development 38.5 ° C 45 seconds 73ml 500ml   Bleaching and fixing 30-35 ° C 45 seconds   Rinse 1 30-35 ° C 20 seconds   Rinse 2 30-35 ° C 20 seconds   Rinse 3 30-35 ° C 20 seconds   Drying 70-80 ° C 60 seconds ──────────────────────────────────── (Note) Replenishment amount * is 1m of photosensitive material^Two The amount per hit. Re
The three-tank three-flow countercurrent system was used. Each processing solution
Is as follows. [0305] ────────────────────────────────────   Color developer Tank solution Replenisher ────────────────────────────────────   Water 700ml 700ml   Sodium triisopropylene (β) sulfonate                                       0.1g 0.1g   Ethylenediaminetetraacetic acid 3.0 g 3.0 g   1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt                                       0.5g 0.5g   Triethanolamine 12.0g 12.0g   6.5 g of potassium chloride None   Potassium bromide 0.03g None   Potassium carbonate 27.0 g 27.0 g   Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical)                                       1.0g 3.0g   Sodium sulfite 0.1g 0.1g   Disodium-N, N-bis (sulfonatoethyl) hydroxylamine                                     10.0g 13.0g   N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-a Minoaniline sulfate 5.0 g 11.5 g   Add water 1000ml 1000ml   pH (25 ° C) 10.0 11.0 ──────────────────────────────────── [0306] ────────────────────────────────────   Bleach-fix solution (the tank solution and the replenisher are the same) ────────────────────────────────────   600 ml of water   Ammonium thiosulfate (700g / l) 100ml   Ammonium sulfite 40g   55 g of iron (III) ammonium ethylenediaminetetraacetate   Disodium ethylenediaminetetraacetate 5g   Ammonium bromide 40g   Nitric acid (67%) 30g   1000 ml with water   pH (25 ° C) (with acetic acid and aqueous ammonia) 5.8 ──────────────────────────────────── The rinsing liquid is ion-exchanged for both the tank liquid and the replenishing liquid.
Exchange water (calcium and magnesium are 3ppm or less each)
Bottom) was used. Table 7 shows the above results. [0308] [Table 7]                                 Table 7 ────────────────────────────────────   Milk dopant sample foot safelight life insurance exposure humidity   Agent Compound Amount (mol / molAg) Number Gradation Safety Presence Dependence ────────────────────────────────────   J None 101 0.23 35 -0.05 -0.08   K K_Three[RhCl₆] 1 × 10^-8  102 0.21 22 -0.10 -0.07   L K_Three[RhCl₆] 2 × 10^-8  103 0.19 12 -0.14 -0.07   M K_Three[RhCl₆] 4 × 10^-8  104 0.17 7 -0.18 -0.06   N K_Two[Ru (NO) Cl_Five] 1 × 10^-8  105 0.20 19 -0.09 -0.07   OK_Two[Ru (NO) Cl_Five] 2 × 10^-8  106 0.18 12 -0.14 -0.06   P K_Two[Ru (NO) Cl_Five] 4 × 10^-8  107 0.17 6 -0.17 -0.06   Q K_Three[Cr (CN)₆] 1 × 10^-8  108 0.21 33 -0.06 -0.04   R K_Three[Cr (CN)₆] 2 × 10^-8  109 0.19 30 -0.06 -0.03   S K_Three[Cr (CN)₆] 4 × 10^-8  110 0.18 28 -0.07 -0.03 ──────────────────────────────────── [Embodiment 8] (Preparation of Emulsion T) 32 g of lime-processed gelatin was added to distilled water 80
0 ml, and dissolved at 40 ° C.
3.3 g was added and the temperature was raised to 70 ° C. continue
A solution prepared by dissolving 100 g of silver nitrate in 400 ml of distilled water
Liquid obtained by dissolving 34.4 g of sodium in 400 ml of distilled water
Was added to the above solution over 43 minutes while maintaining 70 ° C.
The mixture was mixed. Next, 60.0 g of silver nitrate was added to 200 ml of distilled water.
Solution and sodium chloride 20.6g and finished
1.0 × 10 per mol of silver chlorobromide^-FiveMole of K_Three
[Fe (CN)₆ ] In 200 ml of distilled water
Was added and mixed over 18 minutes while maintaining 70 ° C.
After cooling to 40 ° C, desalting and washing with water,
After adding 90 g of ratine and raising the temperature to 50 ° C.,
The used red-sensitizing sensitizing dye G was used per mole of silver halide.
4 × 10^-FiveMole, then add one mole of the finished silver chlorobromide.
1.2 × 10 per le^-6K equivalent to mole_Two [IrCl
₆ ] Containing silver bromide fine grain emulsion (average grain size of 0.1
05 μm) in such an amount that the silver bromide content becomes 1.0 mol%.
did. Furthermore, gold-sulfur sensitization was optimally performed. Like this
Silver chlorobromide emulsion (containing 1.0 mol% of silver bromide)
Emulsion T was used. (Preparation of Emulsion U) In the preparation of Emulsion T,
1.5 × 10 per mol of finished silver chlorobromide^-8Mole
K_Three [RhCl₆ ] To the second addition of sodium chloride
A silver chlorobromide emulsion was prepared in the same manner as in
This was designated as Emulsion U. (0311)Emulsion VPreparation of In the preparation of Emulsion T, 1 mol equivalent of the finished silver chlorobromide
1.5 × 10^-8Mole of K_Three [Cr (CN)₆ ]
That it was added to the sodium chloride solution
A different silver chlorobromide emulsion was prepared and used as emulsion V. The emulsions T to V thus prepared were
The particle shape, particle size,
And particle size distribution were determined. Particle size is particle projection
Expressed as the average of the diameter of the circle equivalent to the area, the particle size
Is the value obtained by dividing the standard deviation of the particle size by the average particle size.
Was used. Emulsions T to V each had a grain size of 0.4
Cubic particles having a particle size distribution of 9 μm and a particle size distribution of 0.09
Was. The X-ray diffraction of emulsions T to V was determined by the silver bromide content.
It shows weak diffraction in the part corresponding to 10 to 40 mol%
Was. In the preparation of the sample 101 of the seventh embodiment,
Added to the photosensitive emulsion layer, green photosensitive emulsion and red photosensitive emulsion layer
1- (5-methylureidophenyl) -5-
The mercaptotetrazole is removed and the milk of the red-sensitive emulsion layer is removed.
Sample 201 was prepared in the same manner except that the emulsion was changed to Emulsion K.
Done. In the preparation of Sample 201, the red photosensitive emulsion layer
The compounds shown in Table 8 were added, and the emulsion in the red-sensitive emulsion layer was
The values were changed as shown in Table 8 and the coating pH was changed to Table 8.
Samples 202 to 202 were prepared in the same manner except that they were changed as shown.
209 was created. Toe gradation and safelight of the sample thus obtained
Safety, raw storage stability and exposure humidity dependency as in Example 7.
I examined it in the same way. The results are shown in Table 8. [0315] [Table 8]                                 Table 8 ────────────────────────────────────     SampleRed photosensitive emulsion layer  Coating pH Foot Safelight Life insurance Exposure humidity           Emulsion additive * Gradation Safety Presence Dependence ────────────────────────────────────   201 T None 5.9 0.23 35 -0.10 -0.08   202 T III-2-2 6.2 0.23 35 -0.05 -0.08   203 T IV-1 5.9 0.22 34 -0.06 -0.08   204 U None 6.0 0.19 13 -0.16 -0.08   205 U III-2-2 5.9 0.20 12 -0.14 -0.07   206 U IV-1 6.1 0.19 13 -0.13 -0.08   207 V None 6.0 0.19 30 -0.09 -0.05   208 V III-2-2 5.8 0.18 33 -0.06 -0.03   209 V IV-1 5.9 0.19 32 -0.07 -0.04   210 V IV-1 4.2 0.20 33 -0.09 -0.04 ──────────────────────────────────── (Note) Additive *: The amount added was 1 mol of silver halide in the red-sensitive emulsion layer.
3 × 10 per le^-FourMole [Embodiment 9] "Preparation of silver bromide cubic emulsion" 36 g of 870 ml of water
Add deionized gelatin and 0.25g of potassium bromide
Dissolved. Stir in this aqueous gelatin solution maintained at 75 ° C
36m of 0.088M silver nitrate aqueous solution (solution 15)
1 and 0.088M aqueous potassium bromide solution (Solution 16) 36
ml for 10 minutes by the double jet method.
Double 176 ml of solution 15 and solution 16 in 7 minutes
It was added by the jet method. Then, 0.82M silver nitrate aqueous solution
1010 ml of liquid (solution 17) was initially 1.8 ml / min
The flow rate was accelerated from the flow rate of
0.90M potassium bromide aqueous solution (Solution 18)
+ 100mV (to the saturated calomel electrode)
Trolled and added. Five minutes after the completion of the addition, the temperature dropped to 35 ° C
After warming and removing the soluble salts by the usual sedimentation method,
And heated to 40 ° C., and 50 g of gelatin was added and dissolved.
Further, sodium chloride and phenol were added, and pH6.
Adjusted to be 5. The obtained particles have a side length of 0.65.
It is a monodispersed silver bromide cube of μm
The number was 10%. [(NH_Four )_Two [RhCl_Five (H_Two O)]
Of silver bromide cubic emulsion doped with silver
In the above, the solution 18 was used for each mole of silver added.
1 × 10^-8, 1 × 10^-7And 1 × 10^-6Mole of (N
H_Four )_Two [RhCl_Five (H_Two O)]
Thus, emulsions were respectively prepared. [K]_Three [Cr (CN)₆ ] Doped odor
Preparation of silver halide cubic emulsion "
18 is 1 × 10 per mole of silver added.^-8,
1 × 10^-7And 1 × 10^-6Mole of K_Three [Cr (CN)
₆ ] Were prepared in the same manner except that
Was. These emulsions were coated in the same manner as in Example 1.
Then, a coated sample was obtained. BPN-42 filters were added to these samples.
Luster (blocks light of 420nm and above)
After giving the exposure for metrology (1 second) through the optical wedge,
After developing with MAA-1 developer at 20 ° C for 10 minutes,
Stop, fix, wash, dry and measure optical density.
Was. Fog was determined at the minimum optical density of the sample. The sensitivity is
The reverse of the exposure required to obtain an optical density of fog +0.5
It is expressed as a relative value and the value in sample 201 is taken as 100
Expressed. The gradation represents the slope of the characteristic curve,
It becomes hard contrast. The foot density is the amount of exposure that gives the above sensitivity.
From the optical density when 0.8 times the exposure amount is given to the minimum optical
Indicates the optical density after subtracting the density.
Indicates a broken leg. The results are shown in Table 9. [0320] [Table 9]                                 Table 9 ────────────────────────────────────   SampleDopant  Fog Sensitivity Gradation Foot density   No.Compound addition amount ──────────────────────────────────── 201 None 0.07 100 2.2 0.35 202 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-8  0.06 67 2.1 0.28 203 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-7  0.06 23 3.0 0.28 204 (NH_Four)_Two[RhCl_Five(H_TwoO)] 1 × 10^-6  0.05 7 3.9 0.25 205K_Three[Cr (CN)₆] 1 × 10^-8  0.06 80 2.3 0.34 206K_Three[Cr (CN)₆] 1 × 10^-7  0.05 57 2.6 0.27 207 K_Three[Cr (CN)₆] 1 × 10^-6  0.05 9 5.7 0.19 ──────────────────────────────────── The above sample numbers 201, 203, 204,
Add 1 mole of silver to the emulsion used to prepare 206 and 207.
9.2 × 10^-6Molar sodium thiosulfate, 2.1
× 10^-6Molar potassium chloroaurate and 2.5 × 10^-Four
Moles of potassium thiocyanate at 60 ° C.
Optimally sensitized by. SoAfter that, apply the same method as above.
Cloth was applied to obtain coating samples 301 to 305, respectively. [0322][Example 11] "K _Three [Fe (CN) ₆ ], K _Three [Ru (CN) ₆ ],
K _Three [Co (CN) ₆ ] Or K _Three [Ir (CN) ₆ ]
Preparation of Cubic Silver Emulsion Doped with Silver " In the preparation of Emulsion A of Example 1, 1 mole of silver halide
1 × 10 per ^-6 Mole of K _Three [Fe (CN) ₆ ], K _Three
[Ru (CN) ₆ ], K _Three [Co (CN) ₆ ] Or K
_Three [Ir (CN) ₆ ] Was added to Solution 4
To prepare a silver halide emulsion. [0323]A sample was prepared and evaluated as in Example 1.
Was. [0324]ConclusionFruitTable 10Shown inTable 10Then,
Sample without loop and K_Three [Cr (CN)₆ ] Dope
The results of the samples obtained are shown again for reference. [0325] [Table 10]Table 10 ────────────────────────────────────   Dopant fog Sensitivity Gradation Foot density ────────────────────────────────────       None 0.06 100 2.6 0.32   K_Three [Cr (CN)₆ ] 0.05 10 5.7 0.07   K_Three [Fe (CN)₆ ] 0.05 99 2.8 0.31   K_Three [Ru (CN)₆ ] 0.05 97 2.7 0.30   K_Three [Co (CN)₆ ] 0.05 95 2.5 0.32   K_Three [Ir (CN)₆ ] 0.05 101 2.6 0.33 ──────────────────────────────────── [Embodiment 12] Each emulsion prepared in Example 11 was added to the emulsion in an amount of 1 × 10
^-2Mole silver bromide fine grain emulsion, 2.5 × 10^-6Mole thio
Sodium sulfate and 3 × 10^-7Add molar chloroauric acid
Then, it was optimally chemically sensitized at 60 ° C. Example 1
It was prepared and evaluated in the same manner as in. The resultTable 11Shown inNo.
11 tablesNow, the undoped sample and K_Three [Cr (C
N)₆ The results of the samples doped with [] are also listed for reference.
You. [0327] [Table 11]Table 11 ────────────────────────────────────   Dopant fog Sensitivity Gradation Foot density ────────────────────────────────────       None 0.10 100 2.2 0.36   K_Three [Cr (CN)₆ ] 0.05 9 6.4 0.15   K_Three [Fe (CN)₆ ] 0.14 50 2.4 0.35   K_Three [Ru (CN)₆ ] 0.05 52 2.3 0.37   K_Three [Co (CN)₆ ] 0.05 73 2.2 0.33   K_Three [Ir (CN)₆ ] 0.05 75 2.4 0.36 ──────────────────────────────────── ─

Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03C 7/00 530 G03C 7/00 530 (56) References JP-A-5-113617 (JP, A) A) JP-A-6-51423 (JP, A) JP-A-6-59376 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/09 G03C 1/035 G03C 1 / 06 501 G03C 7/00 510 G03C 7/00 520 G03C 7/00 530

Claims (1)

(57) Claims 1. A surface latent image type silver halide photographic material having at least one surface latent image type silver halide emulsion layer on a support, wherein the emulsion layer A surface latent image type silver halide photographic material, wherein the surface latent image type silver halide grains contain a cyanochrome complex ion represented by the following formula (I). (I) [Cr (CN) _6-n L _n ] ^{m- wherein} L is H ₂ O or OH, n is 0 or 1, and m is 3 or 4.