JPH0830860B2 - Method for producing silver halide photographic emulsion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a silver halide photographic emulsion which is highly sensitive, stable, and capable of rapid processing.

(Prior Art) With the spread of color photographic materials, color development processing has become simpler and faster, and on the other hand, high quality images and uniformity of finish quality are required. It is generally known that a silver iodobromide emulsion containing 4 to 20 mol% of silver iodide is used for a photographic color photographic material and a silver chlorobromide emulsion is used for a color print material. The silver chlorobromide emulsion has higher sensitivity than the silver iodobromide emulsion and it is difficult to obtain a high quality image, but it is known that it is advantageous for speeding up the color development processing.

Silver chloride or silver chlorobromide, especially cubic particles having a (100) face, is extremely advantageous especially for rapid and simple processing.
It has the drawbacks of low sensitivity, difficulty in chemical sensitization and spectral sensitization, unstable sensitivity, and easy fog. There have been some suggestions on how to solve this. For example, as described in JP-A-48-51627 and JP-B-49-46932, a method of adding a water-soluble bromine ion or iodine ion after adding a sensitizing dye to a silver halide emulsion; As described in JP-A-58-108533, JP-A-60-222845, etc., bromine ions and silver ions are simultaneously added to a silver halide grain having a high silver chloride content to obtain 60 mol on the surface of the grain. % Silver bromide regions;
Similarly, a method of forming a layer of 10 mol% to 50 mol% of silver bromide on the surface of the grains; JP-B-50-36978 and JP-B-58-24077.
No. 2, U.S. Pat.No. 4471050, OLS-3229999, and the like, by adding bromine ion to silver halide having a high silver chloride content or by simultaneously adding bromine ion and silver ion A method for producing particles having a multi-phase structure such as double structure particles or bonded structure particles is known.

(Problems to be solved by the invention) However, each of the methods has many problems such as sensitivity, stability thereof, further decrease in sensitivity due to added color coupler, utilization efficiency of silver halide, tightness of gradation in shade portion. Defects have been found. It is also known that these silver halide emulsions are unstable and difficult to manufacture. This is the case, for example, in the Journal of Phtographic Scienc by Zuckerman.
e ” 24 142 (1976). It can be said that no commercial color light-sensitive material using this method has actually improved the above defects. The present invention seeks to remedy these deficiencies. A first object of the present invention is to provide a method for producing a silver halide photographic emulsion which is advantageous for rapid and simple processing, has high sensitivity and is stable. The second object is to provide a method for producing a silver halide emulsion for color photographic use, which has a good gradation of the shade and has a high utilization efficiency of silver halide, and hence requires a small amount of coated silver.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have found that cubic or tetradecahedral silver halide host grains have an average grain size smaller than that of the silver halide host grains and have a bromide content. It has been found that a silver halide photographic emulsion satisfying the above objects can be produced by mixing silver halide fine grains having a high silver content (mol%) and then ripening.

 The production method of the present invention will be described in detail below.

The production method of the present invention is similar to Ostwald ripening at first glance in that silver halide host grains and fine grain silver halide having a smaller average grain size are mixed and then ripened, but the odor of fine grain silver halide is The recrystallization reaction occurs due to the fact that the silver halide content is higher than that of the host grain, and further, by adsorbing the compound described below on the (100) plane of the host grain, The difference is that the starting point is controlled.

The host silver halide crystals used in the method for producing the photographic emulsion of the present invention are substantially cubic (100) cubic or 14
They are faceted crystal grains (these may have rounded corners and may have a higher order surface) and have a halogen composition of silver bromide or chlorobromide containing 2 mol% or less of silver iodide. Silver or silver chloride, preferably a silver halide crystal containing at least 5 mol% of silver chloride, more preferably 80 mol%
And particularly preferably a silver halide crystal containing at least 99 mol% of silver chloride or a pure silver chloride crystal. The average grain size of the host silver halide grains is preferably 0.
The distribution is preferably monodisperse in the range of 2 μm to 2 μm.

The monodisperse emulsion according to the present invention is an emulsion having a grain size distribution with a variation coefficient (S /) relating to the grain size of silver halide grains being 0.25 or less. Here, the average particle size, S, is the standard deviation related to the particle size. That is, when the grain size of each emulsion grain is ri and the number is ni, the average grain size is And its standard deviation S is Is defined as

The term “individual grain size” as used in the present invention means a silver halide emulsion.
TH James et al. "The Theory of the Photographic Proc
ess ”, 3rd edition, pp. 36-43, published by Macmillan, Inc. (1966), the area projected when microscopically photographed by methods well known in the art (usually electron microscopy). It is the equivalent projected area equivalent diameter. Here, the projected equivalent diameter of a silver halide grain is defined by the diameter of a circle equal to the projected area of a silver halide grain as shown in the above-mentioned book. Therefore, even when the silver halide grains have a shape other than spherical (for example, cubic, octahedral, tetradecahedral, tabular, and potato-like), the average grain size and its deviation S can be obtained as described above.

The coefficient of variation relating to the particle size of the silver halide grains is 0.25 or less, preferably 0.20 or less, more preferably 0.15
Hereafter, it is most preferably 0.10.

The compounds described below are adsorbed on the (100) plane of the above host silver halide grains.

Examples of the adsorptive compound used in the present invention include cyanine dyes, merocyanine dyes, mercaptoazoles (specific examples thereof include general formula (XXI) and (X
XII), compounds represented by (XXIII)), nucleic acids and nucleic acid degradation products (for example, products of deoxyribonucleic acid and ribonucleic acid in the course of decomposition, adenine, guanine, uracil, cytosyl, thymine, etc.), Particularly preferred are compounds represented by the following general formula [I], [II] or [III].

General formula [I] In the formula, Z ₁₀₁ and Z ₁₀₂ each represent an atomic group necessary for forming a heterocyclic nucleus.

As the heterocyclic nucleus, a 5- to 6-membered ring nucleus containing a nitrogen atom and a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom as a hetero atom (a condensed ring may be further bonded to these rings) Or a substituent may be further bonded).

Specific examples of the heterocyclic nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benz Imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, benzotelrazole nucleus, naphthoterrazole nucleus, etc. it can.

R ₁₀₁ and R ₁₀₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. Each of these groups and the groups described below are used in the meaning including the substitution product. For example, taking an alkyl group as an example,
It includes unsubstituted and substituted alkyl groups, which may be linear, branched or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Further, specific examples of the substituent of the substituted alkyl group include a halogen atom (chlorine, bromine, fluorine, etc.), a cyano group, an alkoxy group, a substituted or unsubstituted amino group, a carboxylic acid group,
Examples thereof include a sulfonic acid group and a hydroxyl group, and one or more of these may be substituted in combination.

Specific examples of the alkenyl group include a vinylmethyl group.

Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

m ₁₀₁ represents a positive number of 0 or 1, 2 or 3. m ₁₀₁
When represents 1, R ₁₀₃ represents a hydrogen atom, a lower alkyl group, an aralkyl group or an aryl group.

Specific examples of the aryl group include a substituted or unsubstituted phenyl group.

 R₁₀₄Represents a hydrogen atom. m₁₀₁Represents 2 or 3
If R₁₀₃Represents a hydrogen atom and R₁₀₄Is a hydrogen atom,
In addition to R, R and R₁₀₂Connect with 5
A 6-membered ring can be formed. Also m₁₀₁But 2
Represents 3 and R₁₀₄Is a hydrogen atom, R₁₀₃Is other
R₁₀₃To form a hydrocarbon ring or heterocycle by linking with
Good. These rings are preferably 5- or 6-membered rings. j₁₀₁, K₁₀₁
Represents 0 or 1 and X ₁₀₁Represents an acid anion and n
₁₀₁Represents 0 or 1.

General formula (II) In the formula, Z ₂₀₁ and Z ₂₀₂ have the same meaning as Z ₁₀₁ or Z ₁₀₂ described above. R ₂₀₁ and R ₂₀₂ have the same meaning as R ₁₀₁ or R ₁₀₂ , and R ₂₀₃ represents an alkyl, alkenyl, alkynyl or aryl group (such as a substituted or unsubstituted phenyl group). m ₂₀₁ is 0,
Represents 1 or 2. R ₂₀₄ represents a hydrogen atom, a lower alkyl group or an aryl group, and when m ₂₀₁ represents 2,
R ₂₀₄ and R ₂₀₄ may combine to form a carbohydrogen ring or a heterocycle. These rings are preferably 5- or 6-membered rings.

 Q₂₀₁Is a sulfur atom, carbon atom, selenium atom or N-R
₂₀₅Represents R₂₀₅Is R₂₀₃Is synonymous with. j₂₀₁, R₂₀₁,
X ₂₀₁And n₂₀₁Each j₁₀₁, K₁₀₁, X ₁₀₁And n
₁₀₁Is synonymous with.

General formula (III) In the formula, Z ₃₀₁ represents an atomic group necessary for forming a heterocycle. As the heterocycle, those described with respect to Z ₁₀₁ and Z ₁₀₂ and specific examples thereof include other thiazolidine, thiazoline, benzothiazoline, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, Cores such as dihydropyridine, dihydroquinoline, benzimidazoline and naphthimidazoline can be mentioned. Q ₃₀₁ is synonymous with Q ₂₀₁ . R ₃₀₁ is R ₁₀₁ or R ₁₀₂
And R ₃₀₂ is synonymous with R ₂₀₃ . m ₃₀₁ has the same _meaning as m ₂₀₁ . R ₃₀₃ has the same _meaning as R _204, and when m ₃₀₁ represents 2 or 3, R ₃₀₃ and another R ₃₀₃ may combine to form a hydrocarbon ring or a heterocycle. j ₃₀₁ is synonymous with j ₁₀₁ .

The silver halide grain size of the fine grain silver halide emulsion used in the present invention governs the supply rate of bromine ions, and its preferable grain size varies depending on the size of the host grain and the halogen composition, but is 0.5 μm or less. Normally used. More preferably, it is 0.3 μm or less.

It is essential that the halogen composition of the fine grain emulsion has a silver bromide content higher than that of the host grains, and a bromide concentration of 50 mol% or more is preferable. More preferably, it is desired to contain 70 mol% or more of bromide.

The fine grain emulsion may optionally contain silver iodide. It is also possible to incorporate ions or compounds of heavy metals such as iridium, rhodium and platinum.

The fine grain emulsion has a silver amount relative to the host silver halide.
It is mixed in the range of 50% to 0.1%. More preferably 0.2
It is used in the range of -20%, particularly preferably 0.2-8%. The mixing temperature can be freely selected between 30 ° and 80 ° C.

The emulsion produced by the production method of the present invention has an extremely high sensitivity because the latent image or the development center is concentrated, the stability is remarkably improved, and the fogging is suppressed without impairing the rapid developability. Stability can be obtained. Also,
Surprisingly, since a high-contrast emulsion is obtained and it excels in pressure resistance, it has the advantages of less pressure desensitization and less fog in the unexposed areas.

The adsorptive compound according to the present invention is characterized in that it can be selected from sensitizing dyes. Particularly useful compounds for the (100) plane can be selected from the compounds represented by the above general formulas [I], [II] or [III] and can function as a sensitizing dye. It is also advantageous for increasing the spectral sensitivity. The discovery of such an excellent combination and its effect is surprising.

Further, it may be used in combination with other sensitizing dyes for higher sensitivity and stability, and may be used in combination with a supersensitizer.

For example, an aminostilbenzene compound substituted with a nitrogen-containing heterocyclic nucleus group (for example, Fuji Photo Film Co., Ltd.)
Japanese Patent Application No. 61-23149 filed on September 30, 1986
Compounds of general formula (I) described in US Pat. No. 8, especially specific compound examples (I-1) to (I-17) and US Pat.
3,390, 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,510).
No.), cadmium salt, azaindene compound and the like. U.S. Pat.Nos. 3,615,613 and 3,61
The combinations described in 5,641, 3,617,295 and 3,635,721 are particularly useful.

Next, specific examples of the adsorptive compounds represented by the general formulas [I], [II] and [III] will be given. However, it is not limited to this.

The silver halide emulsion in the present invention is manufactured by a process in which the pH and the time of addition of silver nitrate, alkali halide and the like are controlled. First, the preferred pH at which the host silver halide grains of the present invention are formed is 2-10. Here, doping or noble metal sensitization (gold sensitization, etc.) can also be performed using salts of rhodium, iridium complex salts, lead and the like. In some cases, sulfur sensitization, for example, thiosulfate, allylthiocarbamide, cysteine or the like can be used for reduction sensitization such as polyamine or stannous chloride.

Next, the adsorbing compound is dissolved in an alcohol such as methanol or a water-miscible organic solvent such as ethyl acetate and added to the host silver halide emulsion. Alternatively, the adsorptive compound may be dispersed in a gelatin aqueous solution or a surfactant aqueous solution and added. This addition amount is 1 silver halide
It is preferably 10 ⁻⁶ to 10 ⁻² mol%, more preferably 10 ⁻⁵ to 10 ⁻³ mol%, per mol. Next, fine grain silver halide grains as described above are mixed, and in the temperature range of 30 to 80 ° C.,
Further, the aging is carried out while appropriately controlling the silver ion concentration range of pAg5 to 10.

Thereafter, if necessary, a sensitizing dye may be additionally added, or a supersensitizer may be added to perform spectral sensitization.

The silver halide emulsion is preferably subjected to the chemical sensitization as described above during or after the recrystallization by the mixed ripening.

Further, a fog inhibitor such as mercaptotriazoles, mercaptotetrazoles and benzotriazoles can be used in combination with the silver halide emulsion.

For rapid development, silver chlorobromide emulsions with high silver chloride content are preferred, and mercapto compounds, nitrobenzotriazole compounds, benzotriazole compounds and other fog inhibitors or stabilizers that strongly adsorb silver halide are used. To be Further, a development accelerator which is usually used, an anti-halation agent, an anti-irradiation agent, a brightening agent and the like can be used in combination.

Particularly preferred stabilizers used in the present invention are represented by the general formula [XXI], [XXII] or [XXIII].

General formula (XXI) In the formula, R represents an alkyl group, an alkenyl group or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. The alkali metal atom is, for example, a sodium atom, a potassium atom or the like, and the ammonium group is, for example, a tetramethylammonium group or a trimethylbenzylammonium group. The precursor is a group which can be X = II or an alkali metal under alkaline conditions and represents, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group or the like.

Of the above R, the alkyl group and the alkenyl group include an unsubstituted group and a substituted group, and further include an alicyclic group. The substituent of the substituted alkyl group includes a halogen atom, nitro group, cyano group, hydroxyl group, alkoxy group, aryl group, acylamino group, alkoxycarbonylamino group, ureido group, amino group, heterocyclic group, acyl group, sulfamoyl group. , Sulfonamide algae degree, thioureido group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, and further carboxylic acid group, sulfonic acid group or salts thereof, and the like.

The ureido group, thioureido group, sulfamoyl group, carbamoyl group and amino group each include an unsubstituted group, an N-alkyl substituted group and an N-aryl substituted group. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and substituents of the alkyl groups listed above.

General formula (XXII) In the formula, M represents a sulfur atom or an oxygen atom, L represents a divalent linking group, and R represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. The alkyl group, alkenyl group and X of R have the same meanings as those in formula [XXI].

Specific examples of the divalent linking group represented by L above include: And combinations thereof.

n represents 0 or 1, and R ⁰ , R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aralkyl group.

General formula (XXIII) In the formula, R and X have the same meanings as those in the general formula [XXI], and L has the same meanings as those in the general formula [XXII]. R ³ has the same meaning as R, and may be the same or different.

General formula [XXI] used in the present invention, general formula [XXII]
Alternatively, the compound represented by the general formula [XXIII] can be contained in any layer in the silver halide color photographic light-sensitive material and / or in the color developing solution. By any layer in a silver halide color photographic light-sensitive material is meant a light-sensitive and light-insensitive hydrophilic colloid layer.

General formula [XXI], general formula [XXII] or general formula [XXII
The addition amount of the compound represented by I] is 1 when the content in the silver halide color photographic light-sensitive material is 1.
1 × 10 ^{−5 to} 5 × 10 ⁻² mol is preferable, and 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol is more preferable per mol. When it is contained in the color developer, it is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol / 1, more preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol / 1.

Specific examples of the compounds represented by the general formula [XXI], the general formula [XXII] and the general formula [XXIII] are listed below, but the invention is not limited thereto. The compounds described on pages 11 to 30-1 of the specification of Japanese Patent Application No. 61-114276 can be mentioned.

The color coupler used in the present invention will be described. In addition to the general requirements such as its color-developing phase and its high extinction coefficient, the development of the silver halide grains of the present invention to be used is particularly fast, so that it can be used as an oxidant of a color developing agent such as a paraphenylenediamine derivative. A highly active color coupler is required so that the coupling coloring reaction is not rate-limiting.
From this viewpoint, it is preferable to use a coupler represented by the following general formula [IV], [V], [VI] or [VII].

General formula (IV) General formula [V] General formula [VI] General formula (VII) General formula [VIII] (In the formula, R ₁ , R ₄ and R ₅ each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, and R ₂ represents an aliphatic group, R ₃ And R ₆ are each a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group,
Or an acylamino group, R ₇ and R ₉ represent a substituted or unsubstituted phenyl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and R ₁₀ Represents a hydrogen atom or a substituent, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and Zb represent methine, substituted methine, or = N-, and Y ₁ , Y ₂ and Y ₄ Represents a halogen atom, or a group capable of splitting off during a coupling reaction with an oxidant with a developing agent (hereinafter abbreviated as splitting group), Y ₃ represents a hydrogen atom or a splitting group, Y ₅ represents a splitting group, In the general formula [IV] and the general formula [V], R ₂ and R ₃ and
R ₅ and R ₆ may form a 5-, 6- or 7-membered ring, respectively.

Furthermore, R ₁ , R ₂ , R ₃ or Y ₁ ; R ₄ , R ₅ , R ₆ or Y ₂ ; R ₇ ,
R ₈ , R ₉ or Y ₃ ; R ₁₀ , Za, Zb or Y ₄ ; Q or Y ₅ may form a dimer or higher multimer.

The above general formulas [IV], [V], [VI], [VII] and [V]
III) in R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
For details of Za, Zb, Q ₁ , Y ₁ , Y ₂ , Y ₃ and Y ₄ , see Japanese Patent Application No. 61-175233 (filed on July 25, 1986 by Fuji Photo Film Co., Ltd.) The same as those of the general formulas (I), (II), (III), (IV) and (V) described in 17th page, 3rd page to 34th page.

Specific examples of these color couplers include (C-1) to (C-40) and (M-1) described on pages 36 to 78 of Japanese Patent Application No. 61-175233. ) ~ (M-42), (Y
-1) to (Y-46) can be mentioned, and more preferably, the following compounds can be mentioned.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

In the light-sensitive material in which the color coupler represented by the above general formula [IV], [V], [VI], [VII] or [VII] is used, the preferable silver halide coating amount is that of the reflection support. If a ^{1.5g / m 2 ~0.1g / m 2} , the case of using the transparent support is a ^{7g / m 2 ~0.2g / m 2} .

These couplers may be dispersed in the emulsion layer in the presence of at least one high boiling point organic solvent. Preferably, high boiling organic solvents represented by the following general formulas (A) to (E) are used.

General formula (A) General formula (B) W _1- COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ -OW ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W ₄ Is W ₁ , OW ₁ or SW
Represents ₁ , and n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (E), W ₁ and W ₂ are condensed rings. May be formed).

Example-1 A silver halide emulsion (A) was prepared as follows.

(1 liquid) (2nd liquid) Sulfuric acid (1N) 24ml (3rd liquid) The following compound A (1%) 3ml (4 solutions) (5 liquids) (6 liquids) (7 liquids) (Liquid 1) was heated to 52 ° C., and (2nd liquid) and (3rd liquid) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 14 minutes. After an additional 10 minutes, (Sixth solution) and (Sixth solution) were added simultaneously for 15 minutes. Five minutes after the addition, the temperature was lowered to desalt.

Water and dispersed gelatin were added, the pH was adjusted to 6.2, and a monodispersed cubic silver chloride emulsion having an average particle size of 0.48 μm and a coefficient of variation (standard deviation divided by average particle size; s / d) of 0.10 was obtained. Sodium thiosulfate was added to this emulsion at 58 ° C. for optimum chemical sensitization, and the above-mentioned CR-24 was added for 4 × 10 ^-4 mol per mol of silver halide to perform spectral sensitization. .
Further, [XXI]-(7) was used as a stabilizer in 1 mol of silver halide.
5 × 10 ^-4 mol was added per liter.

For emulsion (A), after adding (6 solution) and (7 solution), (8 solution) below was added over 10 minutes, and then 5
Emulsion (B) was prepared after a minute
And

(8 liquids) Emulsion (A) was prepared by adding the following (9 solutions) and (10 solutions) instead of (6 solutions) and (7 solutions) for 15 minutes, and after 10 minutes, (11 liquid) and (12
Liquid) was added over 5 minutes, and 5 minutes later, an emulsion (C) different in that the temperature was lowered was prepared.

(9 liquid) (10 liquid) (11 liquids) (12 liquids) Next, instead of (11 liquid) and (12 liquid) of emulsion (C),
Emulsion (D) was prepared by using the following (13 solution) and (14 solution), respectively.

(13 liquids) (14 liquids) Subsequently, the emulsion (A) is a silver bromide ultrafine grain emulsion (grain size 0.05 μ) to silver chloride before chemical sensitization.
An emulsion (E) was prepared which was different in that it was added in an amount containing 1 mol% of silver bromide and ripened at 58 ° C. for 10 minutes.

Furthermore, emulsion (E) means CR-24 (silver halide 1 mol
An emulsion (F) was prepared which was different from that of the silver bromide ultrafine grain emulsion in the amount of 4.0 × 10 ^-4 mol) added.

Next, 100 g of the magenta coupler (M- (1) described above) was mixed with 80 g of the color image stabilizer (Cpd-3) and 38 g of (Cpd-4) as a solvent (So.
lv-2) dissolved in a mixed solution of 130 ml and ethyl acetate 100 ml,
4.0 g of this solution is sodium dodecylbenzene sulfonate.
Was emulsified and dispersed in 1200 g of a 10% gelatin aqueous solution containing a to prepare an emulsified dispersion (A). The chemical structure of the compound used is
It is as follows.

Six kinds of samples having the contents shown in Table 1 were prepared in total. The polyethylene on the side coated with the emulsion and protective layers contains titanium dioxide and traces of ultramarine blue. As a hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following experiments were conducted to examine the photographic characteristics of these coated samples.

First, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used for the coated sample, and gradation exposure for sensitometry was given through a green filter. The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 1/10 second.

 Then, the following color development processing was performed.

(Processing process) (Temperature) (Time) Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Water wash 28-35 ° C 90 seconds Color development solution Triethanolamine 8.12g N, N-diethylhydroxylamine 4.93g Fluorescence enhancement Whitening agent (UVITEX CK manufactured by Ciba-Geigy) 2.80 g 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine sulfate 4.96 g sodium sulfite 0.13 g Potassium carbonate 18.40g Potassium hydrogen carbonate 4.85g EDTA ・ 2Na ・ 2H O 2.20g Sodium chloride 1.36g Add water 1000ml pH 10.05 Bleach-fix solution Ammonium thiosulfate (54wt%) 103.0ml NH 〔EDTA ・ Fe〕 54.10ml EDTA ・2Na ・ 2H 2 O 3.41g Sodium sulfite 16.71g Glacial acetic acid 8.61g Water was added to 1000ml pH 5.44 The color density of each sample was measured and the sensitivity and gradation were obtained. The sensitivity was defined as the reciprocal of the exposure amount that gives a color density 0.5 higher than the fog density, and was expressed as a relative value when the sensitivity of Sample 101 is 100. The gradation was represented by the difference between the logarithm of the exposure amount giving a color density of 0.5 and the logarithm of the exposure amount giving a color density of 2.0.

 The results are summarized in Table 2.

From this, it is clear that the emulsion of the present invention can provide a light-sensitive material having high sensitivity and high contrast as compared with other methods.

Example-2 A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The respective preparation methods are described below.

Preparation of coupler emulsion 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 4.4g ethyl acetate 27.2CC and solvent (Solv-1) 7.7
CC was added and dissolved, and this solution was emulsified and dispersed in a 10% gelatin aqueous solution 185CC containing 10% sodium dodecylbenzenesulfonate 8CC.

Thereafter, each emulsion for magenta, cyan and intermediate layers was prepared in the same manner.

 The compounds used for each emulsion are shown below.

(ExM1) Same as M- (1) above.

(ExM2) Same as M- (3) above.

(ExC1) Same as C- (1) above In the blue-sensitive emulsion layer, a stabilizer (the above [XXI]-
(7)) was added at 2.5 × 10 ⁻⁴ mol per mol of silver halide.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following dyes were added to the emulsion layer to prevent irradiation.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Next, a method for preparing the emulsion used in this example is shown.

The blue-sensitive emulsion is prepared by using the emulsion (G) prepared by the following method.
Used as the emulsion of the present invention.

<Preparation method of emulsion (G)> Formation of silver chloride host grains (1 liquid) (2 solutions) Sulfuric acid (1N) 24CC (3 solutions) The following compound A (1%) 3CC (4 solutions) (5 liquids) (6 liquids) (7 liquids) (Liquid 1) was heated to 76 ° C., and (Liquid 2) and (Liquid 3) were added.

Then, (4 solution) and (5 solution) were added simultaneously spending 10 minutes.

After another 10 minutes, (6 solution) and (7 solution) were added simultaneously spending 35 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Water and dispersed gelatin were added to adjust the pH to 6.3 to obtain a monodispersed cubic silver chloride emulsion having an average grain size of 1.1 μm and a coefficient of variation (standard deviation divided by average grain size: s / d) of 0.10.

Take 1/2 of this emulsion and, on the other hand, use a 0.6% solution of the blue spectral sensitizing dye (CR-7 above) as an adsorbing compound at 12.6C.
C, and then 0.05 μg of AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol% relative to the host AgCl emulsion, and the mixture was added at 58 ° C.
Mixed and aged for 0 minutes. After that, sodium thiosulfate was added to optimally carry out chemical sensitization, and the stabilizer ([XXI]
-(7)) was added at 10 ^-4 mol / mol Ag. This is designated as emulsion (G), and the emulsion to which the rest of the adsorptive compound is not added is added to the emulsion at 58 ° C. in the same amount as the above-mentioned AgBr ultrafine grain emulsion and mixed and aged for 10 minutes. After emulsion sensitization and completion of chemical sensitization, CR-7 was added at a ratio of 2.6 × 10 ⁻⁴ mol / mol Ag to prepare an emulsion (H).

As the green-sensitive emulsion, the emulsions (E) and (F) prepared in Example-1 are used.

For the red-sensitive emulsion, the sensitizing dye used as the CR compound in the method for preparing the green-sensitive emulsions (E) and (F) was CR-32.
And the addition amount is 1.5 × 10 ^-4 per mol of silver halide.
Emulsions (J) and (K) were prepared in exactly the same manner except that the moles were used.

Samples were applied in combination as shown in Table 3
201-208 were produced.

 All couplers were replaced on an equimolar basis.

(Layer Structure) The composition of each layer in Sample 201 is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the 1st layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] 1st layer (blue sensitive layer) Silver halide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.36 Gelatin 1.24 Magenta coupler (ExM1) 0.31 Color image stabilizer (Cpd-3) 0.25 Color image stabilizer (Cpd-4) 0.12 Solvent (Solv-2) 0.42 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1 ) 0.62 Anti-color mixing agent (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red sensitive layer) Silver halide emulsion 0.23 Gelatin 1.34 Cyan coupler (blend of ExC1 and C2, 1: 1) 0.34 Color image stability Agent (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) 0.23 Sixth layer (UV absorbing layer) Zera Down 0.53 UV absorber (UV-1) 0.21 solvent (Solv-3) 0.08 Seventh Layer (protective layer) Gelatin 1.33 Polyvinyl acrylic modified copolymer of an alcohol (modification degree
17%) 0.17 Flowing paraffin 0.03 The obtained coating samples 201 to 208 were subjected to color development processing in accordance with the processing solutions and processing steps shown in Example-1, and the sensitivity of each of the blue-sensitive, green-sensitive and red-sensitive layers was improved. I made a comparison. The results obtained are shown in Table 4.

As is clear from the results shown in Table 4, it can be seen that the combination of the present invention is remarkably sensitized with respect to the comparative example.

Example 3 Sample 301, which is a multilayer color light-sensitive material having each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

1st layer (anti-halation layer) Black colloidal silver …… 0.2 Gelatin …… 1.3 Colored coupler C-1 …… 0.06 UV absorber UV-1 …… 0.1 Same as above UV-2 …… 0.2 Dispersion oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.01 Second layer (intermediate layer) Fine silver chloride (average particle size 0.07μ) …… 0.15 Gelatin …… 1.0 Colored coupler C-2 …… 0.02 Dispersion oil Oil-1 …… 0.1 Third layer (First red-sensitive emulsion layer) Emulsion (1) As shown in Table 5 (Average grain size 0.4μ, fluctuation rate 0.12) ...... Silver 1.0 sensitizing dye I ...... 1.5 × 10 ^-4 sensitizing dye II ...... 3.5 × 10 ^-4 Sensitizing dye III …… 1.5 × 10 ^-5 Coupler C-3 …… 0.48 Coupler C-4 …… 0.48 Coupler C-8 …… 0.08 Coupler C-2 …… 0.08 Dispersion oil Oil-1 …… 0.30 Same as above Oil-3 ...... 0.04 4th layer (second red-sensitive emulsion layer) emulsion (2) (average particle size 0.7 .mu.m, variation rate 0.10) sensitized ...... silver 1.0 gelatin 1.0 dye I ...... 1 × 10 ^{- 4} increase Dye II ...... 3 × 10 ^-4 Sensitizing dye III ...... 1 × 10 ^-5 coupler C-6 ...... 0.05 Coupler C-7 ...... 0.1 dispersion oil Oil-1 ...... 0.01 ditto Oil ...... 0.05 Fifth Layer (Intermediate layer) Gelatin …… 1.0 Compound Cpd-A 0.03 Dispersion oil Oil-1 …… 0.05 6th layer (1st green emulsion layer) Emulsion (3) As shown in Table 5 (Average grain size 0.4μ, fluctuation rate) 0.12) …… Silver 0.8 Sensitizing dye IV …… 5 × 10 ^-4 Sensitizing dye V …… 2 × 10 ^-4 Coupler C-9 …… 0.50 Coupler C-1 …… 0.06 Coupler C-10 …… 0.03 Coupler C-5 ...... 0.02 Dispersion oil Oil-1 0.4 Seventh layer (second green emulsion layer) Emulsion (4) As shown in Table 5 (average grain size 0.7μ, fluctuation rate 0.10) ...... Silver 0.85 gelatin ...... 1.0 Sensitizing dye VI …… 3.5 × 10 ^-4 Sensitizing dye V …… 1.4 × 10 ^-4 Coupler C-11 …… 0.01 Coupler C-12 …… 0.03 Coupler C-13 …… 0.20 Coupler C-1 …… 0.02 Coupler C-15 …… 0.02 Dispersion oil Oil-1… 0.20 Same as above Oil 0.05 Eighth layer (yellow filter layer) Gelatin …… 1.2 Yellow colloidal silver …… 0.08 Compound Cpd-B …… 0.1 Dispersion oil Oil-1 …… 0.3 Ninth layer (first blue emulsion layer) Emulsion ( 5) As shown in Table 5 (average particle size 0.4μ, fluctuation rate 0.12) …… Silver 0.4 Gelatin …… 1.0 Sensitizing dye VI …… 2 × 10 ^-4 Coupler C-14 …… 0.9 Coupler C-5 …… 0.07 Dispersion oil Oil-1 …… 0.2 10th layer (2nd blue emulsion layer) Emulsion (6) As shown in Table 5 (average grain size 0.7μ, fluctuation rate 0.10) …… Silver 0.5 gelatin …… 0.6 Sensitization Dye VI …… 1 × 10 ^-4 coupler C-14 …… 0.25 Dispersion oil Oil-1 …… 0.07 11th layer (1st protective layer) Gelatin …… 0.8 UV absorber UV-1 …… 0.1 Same as UV-2 …… 0.2 Dispersed oil Oil-1 …… 0.01 Dispersed oil Oil-2 …… 0.01 12th layer (second protective layer) Fine silver chloride (average particle size 0.07μ) …… 0.5 Gelatin …… 0.45 Polymethylmethacry Over door particles (diameter 1.5μ) ...... 0.2
Hardener H-1 ... 0.4 Formaldehyde scavenger S-1 ... 0.5 Formaldehyde scavenger S-2 ... 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared as described above is used as sample 201.
And

The chemical structural formulas or names of the compounds used in the present invention are shown below: Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate CpdB Same as Cpd-2 above Sensitizing dye II Same as CR-11 above Sensitizing dye III Same as CR-12 above Sensitizing dye IV Same as CR-24 above Next, in Sample 301, the third layer emulsion (1), the fourth layer emulsion (2), the sixth layer emulsion (3), the seventh layer emulsion (4), the ninth layer emulsion (5), Emulsions (6) for the 10th layer were changed to the emulsions shown in Table 5 to prepare samples 302 to 304. The characteristics such as physical properties of each emulsion are shown in Table 6.

In Samples 303 and 304, a sensitizing dye is used as the adsorptive compound. The method for preparing the emulsions used for Samples 301 to 304 is as follows.

[Preparation of Emulsions (1) to (6)] In the method for preparing Emulsion A of Example-1, the grain size is changed by changing the temperature at the time of grain formation, and sodium thiosulfate is used for optimum chemical increase. Feel the emulsion (1) ~
(6) was obtained.

[Preparation of emulsions (7) to (12)] Grains are formed in the same manner as emulsions (1) to (6), and sodium thiosulfate, chloroauric acid and ammonium rhodanate are added during chemical ripening to prepare emulsions (7) to (). 12) got.

[Emulsions (13) to (18)] Particles were formed in the same manner as in the emulsions (1) to (6).
After adding an adsorbing compound in the same manner as in No. 1, ultrafine AgBr
(0.05μ) by adding 2 mol% per mol of silver halide
After mixing and ripening at 58 ° C. for 10 minutes, sodium thiosulfate was added to perform optimum chemical ripening to obtain emulsions (13) to (18).

[Emulsions (19) to (24)] Emulsions (13) to (18) were chemically ripened by adding chloroauric acid and rhodan ammonium in addition to sodium thiosulfate, and then emulsions (19) to (24). ) Got.

These photographic elements were exposed to 25 CMS for 1/100 seconds with a tungsten light source and a filter adjusted to a color temperature of 4800 ° K and then developed at 38 ° C according to the processing steps described below.

Color development 2 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4- (N-ethyl-N-β -Hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0l pH10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0l pH6.6 Stabilizer Holimarin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g For samples 301 to 304 treated with 1.0 l of water, the concentration was measured with red light, green light and blue light. The results obtained are shown in Table 7.
In Table 7, the relative sensitivity means the relative value of the exposure amount required to give a density equivalent to [minimum density + 0.2] expressed as a true number.

From Table 7, the sample 303 of the present invention has an extremely high sensitivity to the comparative examples 301 and 302, and the sample 304 chemically sensitized with chloroauric acid has a higher sensitivity, and the effect of the present invention is clear. .

(Effect of the Invention) According to the production method of the present invention, it is possible to obtain a silver halide photographic emulsion in which the intrinsic sensitivity region is remarkably enhanced and the stability thereof is improved.

Further, even if a high-temperature rapid treatment is performed, fog is low and excellent stability can be obtained.

Further, since a high-contrast emulsion is obtained and pressure resistance is excellent, there is an advantage that pressure desensitization is small and fog in an unexposed area due to pressure is small.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Keisuke Shiba, 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. Mitsuo Suma (56) References JP 61-50134 (JP, A) JP A 61-279848 (JP, A) JP-A-48-89722 (JP, A) JP-A-59-48756 (JP, A) JP-A-59-148050 (JP, A) JP-A-61-133941 (JP, A)

Claims (2)

[Claims] 1. A cubic or tetradecahedral silver halide host.
The emulsion grains have a silver chloride content of at least
95 mol% and the average particle size is only 0.2-2μ
Silver halide host emulsion whose grain size distribution is monodisperse
The particles are represented by the following general formula [I], [II] or [III].
(100) face of the host emulsion grains by adding the compound
And the average particle size is smaller than the host emulsion particles.
And a silver bromide content higher than that of the host grains.
Mixed silver halide emulsion containing fine silver chlorobromide grains
Of a silver halide photographic emulsion characterized by aging and aging
Manufacturing method. General formula [I]Where Z₁₀₁And Z₁₀₂Are each required to form a heterocyclic nucleus
Represents an atomic group. R₁₀₁And R₁₀₂Is an alkyl group, alk
It represents a nyl group, an alkynyl group or an aralkyl group. m
₁₀₁Represents an integer of 0 or 1, 2 or 3 m₁₀₁
Is 1 then R₁₀₃Is a hydrogen atom, lower alkyl
Group, aralkyl group, aryl group₁₀₄Is a hydrogen atom
Represents m₁₀₁Is 2 or 3, then R₁₀₃Is hydrogen
Represents an atom R₁₀₄Is a hydrogen atom, lower alkyl group, aral
Represents a kill group R₁₀₂Form a 5- to 6-membered ring by connecting with
can do. Also m₁₀₁Represents 2 or 3 and R₁₀₄
Is a hydrogen atom, R₁₀₃Is another R₁₀₃Connected with charcoal
A hydrogen ring or a heterocycle may be formed. j₁₀₁, K₁₀₁Is
Represents 0 or 1 and X ₁₀₁Represents an acid anion and n
₁₀₁Represents 0 or 1. General formula (II)Where Z₂₀₁, Z₂₀₂Is the above Z₁₀₁Or Z₁₀₂Is synonymous with.
R₂₀₁, R₂₀₂Is R₁₀₁Or R₁₀₂Is synonymous with R₂₀₃Is Archi
Represents alkenyl, alkenyl, alkynyl or aryl.
m₂₀₁Represents 0, 1 or 2. R₂₀₄Is a hydrogen atom, lower
Represents an alkyl or aryl group, m₂₀₁Represents 2
R₂₀₄And R₂₀₄And are linked to form a carbon-hydrogen ring or heterocycle
May be formed. Q₂₀₁Is sulfur atom, oxygen atom, selenium
Atom or N-R₂₀₅Represents R₂₀₅Is R₂₀₃Is synonymous with
You j₂₀₁, R₂₀₁, X ₂₀₁And n₂₀₁Each j₁₀₁,
k₁₀₁, X ₁₀₁And n₁₀₁Is synonymous with. General formula (III)Z₃₀₁Represents an atomic group necessary for forming a heterocycle. Q₃₀₁
Is Q₂₀₁Is synonymous with. R₃₀₁Is R₁₀₁Or R₁₀₂And R₃₀₂Is
R₂₀₃Is synonymous with. m₃₀₁Is m₂₀₁Is synonymous with. R₃₀₃Is
R₂₀₄Synonymous with m₃₀₁R is 2 or 3₃₀₃
And other R₃₀₃And are linked to form a hydrocarbon ring or heterocycle
May be. j₃₀₁Is j₁₀₁Is synonymous with. 2. A method for producing a silver halide photographic emulsion according to claim 1, wherein a color coupler is further added after ripening.