JPH02110540A - Silver halide photosensitive material having good preservable property - Google Patents

Abstract

PURPOSE:To improve the preservable property under high temp. and high humidity by growing the particles of emulsion layers contg. photosensitive silver halide particles in the presence of a silver halide solvent which is a sulfur-bearing compd. and redispersing silver iodide particles therein to form the silver iodide-contg. silver halide particles incorporated into the particles. CONSTITUTION:This photosensitive material has at least one layer of the emulsion layers contg. the photosensitive silver halide particles on the supporting body. These particles are grown in the presence of the silver halide solvent which is the sulfur- bearing compd. and the silver iodide particles are redispersed therein to constitute the silver halide photosensitive material as the silver iodide-contg. silver halide particles incorporated into the particles. Namely, the silver iodide which is most hardly soluble as the photosensitive silver halide particle stock is added in the form of particles or is formed as precedent precipitate, but these silver iodide particles redisperse into the grown particles and are uniformly incorporated therein without acting as the settling nuclei of the silver halide to be additionally formed. The preservable property after aging, particularly the aging at and under a high temp. and high humidity and particularly sensitivity preservable property are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photosensitive material whose silver halide phase has been converted by a solid phase heterogeneous reaction.

(Background of the Invention) In response to demands for higher sensitivity and higher image quality of silver halide photosensitive materials, many technological efforts have been made to develop an emulsion layer consisting of core/shell type silver iodobromide grains containing high silver iodide. Silver halide photosensitive materials have been proposed.

However, these photosensitive materials have problems in retaining their properties over time, especially when exposed to high temperature and humidity, resulting in a decrease in sensitivity. The problem seems to include the internal structure of the particles.

The production and growth of silver halide grains, particularly the growth and preparation of silver halide grains into a core/shell type, can be roughly divided into two types depending on the form of grain growth.

One of them is to generate new silver halide (hereinafter referred to as AgX) as amorphous microparticles in a suspension medium, and to investigate the local fluctuations in the formation conditions in the suspension medium during the new generation of the microparticles and/or Alternatively, the particles may grow by natural selection, depending on the cohesiveness and solubility product between microparticles whose size has changed relative to the time-series difference in generation time, and the difference in dissolution pressure determined by the particle size. This is a method in which growth is led by solution pressure as the surface activity against aggregation is exhausted, and is referred to as the solution pressure method.

The growth process using only solution pressure is particularly called Ostwald ripening.

It is thought that each AgX crystal particle produced by this method undergoes annealing, dislocations and other crystal defects are sorted out, and a regular equilibrium is reached, but when looking at the particles, the particle distribution inevitably changes. It is difficult to guarantee uniformity in the composition ratio and crystal form of each AgX contained.

Another growth mode is a crystal nucleation method in which existing amorphous fine grains or crystal grains in a suspension medium are used as crystal growth nuclei, and newly formed AgX is adhered or precipitated on the surface to cover and enlarge the existing grains. Grain growth is necessarily at least 2
Stages - Numerically, this is carried out by supplying the nascent AgX in multiple stages or continuously in proportion to the total surface area of the existing particles.

In this method, not only particles that already have a stable size, but also
Ag that causes the next generation of even the first generation of primitive micrograins
For X, I) Ag acts as a crystal growth nucleus by adjusting the production rate or pI4, and it is possible to provide a group of particles grown with almost uniform size.

If a crystal control agent is also used during the period of supplying new AgX to crystal growth nuclei, the crystal phase can be selected quite freely.

The crystal nucleus method is also convenient for preparing core/shell type particles.

As a method for producing an emulsion, one is free to choose an intermediate method among the typical methods described above, depending on the purpose.

During the manufacturing process of these emulsions, reaction by-products, excess compounds, and additives dissolved in the emulsion are removed if they adversely affect subsequent steps or property design. For removal, modern emulsion technology generally chooses coagulation methods using flocculants.

Among the typical methods described above, emulsions thickened by the solution pressure method are
Variations in the composition ratio of X and differences in grain surface conditions cause differences in light acceptance rate, quantum efficiency, adsorption of additives, and developability, resulting in large variations in the performance of the final finished emulsion.

In addition, emulsions thickened by the crystal nucleation method can form monodisperse grain groups with uniform grain sizes and composition ratios among the grains, and whose characteristics can be easily controlled, resulting in good reproducibility. In recent years, when the demands on the quality of life have become high and strict, it has been widely praised.

However, monodispersed emulsions obtained using conventional seed emulsions of the crystal nucleus method are susceptible to thermal fog and pressure fog when moved, have poor adsorption of sensitizing dyes, and tend to have a soft tone, and also have high iodine. As mentioned above, core/shell type silver iodobromide photosensitive materials containing silver oxide suffer from poor storage stability under high temperature and high humidity conditions.

(Object of the Invention) An object of the present invention is to provide a silver halide photosensitive material that has good storage stability over time, particularly when aged under high temperature and high humidity conditions, particularly good sensitivity storage stability.

(Means for Achieving the Object of the Invention) As a result of examination in accordance with the above object, it was found that the present invention has an emulsion layer containing at least one photosensitive silver halide grain on a support, and the grain is a sulfur-containing compound. The object of the present invention is to construct a silver halide photosensitive material as legalized silver halide grains grown in the presence of a silver halide solvent and in which silver iodide grains are redispersed and incorporated into the grains. was achieved.

(Structure and Effects of the Invention) In the present invention, silver iodide, which is the least soluble as a material for photosensitive silver halide grains, can be added as grains or produced as precipitate. Moreover, the silver iodide already has an average grain size of 0.7 μm or less, preferably 0°005 to 0.3 μm.
It has a particle size of However, these silver iodide grains do not act as precipitation nuclei for additionally produced silver halide, but are redispersed and uniformly incorporated into the growing grains. This phenomenon has already been reported in Japanese Patent Application No. 62-333934.
-44571 etc.

This phenomenon is difficult to understand simply from the solubility product and the solubility pressure based on the solid-liquid phase heterogeneous reaction.

It is still unclear whether the solid phase-solid phase heterogeneous reaction according to the present invention is caused simply by diffusion or by crystal destruction,
It seems necessary to consider the general system entropy from a reciprocal perspective.

In the present invention, this phenomenon is referred to as halogen phase conversion.

Regarding the redispersion of silver iodide in the halogen silver shell layer of the grains formed by the next generation of halogen silver, X-ray diffraction, EPMA (
Electron-Probe Micro-Anal
ysis) method, XMA measurement method, or X-ray photoelectron spectroscopy.

Furthermore, in addition to the above-mentioned halogen phase conversion, the present invention enhances the desired effect by applying a silver halide solvent, which is a gold-containing metal, during the growth of silver halide grains.

Ammonia is still insufficiently effective as a silver halide solvent, and therefore, in the present invention, a metal oxide is selected.

The Kinzo compound of the silver halide solvent will be specifically explained.

The Kinzo compound according to the present invention has the following formula (I) (II
') and (III).

General formula CI) 11I represents C-1 or -CO-, in which at least one is a sulfur atom. Here, when m is 2 or more, X and R1 may be the same or different. Preferably, the number of sulfur atoms represented by X is two or more.

m is O or an integer of 1-5, preferably an integer of 1-5.

R1 is an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 to 5 carbon atoms, and specific examples thereof include dimethylene group, trimethylene group, tetramethylene group, and methylethylene group.

R, , R represents an unsubstituted or substituted alkyl group, R2,
R1 may be the same or different, but always one is a substituted alkyl group, and the substituent is -COOM.

SO3M, NRJsRs・Zo, OH, OH2, C
0NIIRs, NHCOR, and -NR,. R11 may be the same or different when at least one substituent is substituted with two or more substituents.

Here, R4, Rs, Rs, R7, and R1 are alkyl groups having 1 to 5 carbon atoms, and R1, R10, and R1
1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

R, , R, , R8 may be the same or different.

M represents a hydrogen atom, an alkali metal, quaternary ammonium or quaternary phosphonium.

Zo represents an anion.

Specific examples of the Kinzo compound in the present invention are shown below.

1100CCL S (Clb)z・5-ctlz
cOOIlNaOxS(C112) )S(C112)
2S(CHz) +SO3NaC,H,5(CHt,
) 2S(CH2) 2NIICO(C1l□), co
onNaOxS(C11z)zS(C)I2)2S(C
l12) zsOxNaNaO3S(CHJzSCCH2
)sSCCHx)zsOsNaNaOxS(C)1t)
zS(C11J2S(Cl12)zS(CIlz)zs
OsNa1100c(Clb)is(C112)zO(
Ct(x)zO(CI□)2S(CH□)2COOHN
aOsS(CtlJtS(Ctlz)zS(CHt)z
S(Cl12)+ SO3NaCHzC(Ctlz)z
S(Cllz)s O (Cll□)3S(CI+
□), COOI+NaOxS (C11.), S
(C112)2cONIIc112N11CO(Cll
z)is(Cl12)zso,Na(C11z)zcO
o(CIlz)2COOH(CL)2COO(CH2)
2COOHNH.

S-16 S-17 S~19 SCN -2O NH, SCN 1O(CHz)zs(CI!2)zs(C1l□)zs
(CI(*)zOHHO(CL)xs(CH2)2s(
Cll□)20H-Formula (n) In the formula, Z is -3(C1(2)ncOOH or -5(Cl
li) ncJOf(, where X represents a sulfur atom or an oxygen atom, a is each 0 or l, b is 0 to 3, C is each O to 2
is an integer, d is 2. Further, n is an integer of 1 to 6. However, this thioether compound contains at least four sulfur atoms.

Specific examples of thioether compounds included within the scope of the present invention are as follows.

C) 125C++, C) 125cII2COI+S-3
6 C1l, Co, e General formula (III) HO, C(C2H,S) 2 (CH2)n(CHR,
)n(CHR2)n (SC2H,) 2Co 2II
In the formula, R is a hydrogen atom, a hydroxy group or -○○OH, R7 is a hydrogen atom or -(CI(□), COOH), and n is each 1 or 2.

Specific examples of thioether compounds included in the scope of the present invention include the following.

110, C (+, H, 5) 2CH, C110IC112
(SC2+1.)2 C02HIO2C(C,H,S)
, CIl, (CtlOH) , CIl□(SC2+14
) zcOzllHOzC(CtH,S) x (CI
l t ) zcH (C1l 2CII2COOH)
(SC2114) zcOzHH02C (CzH4S)
, (CHz)yo(CFICOOH)i(CI□) 1(
SC21L)zcOzH110zc(C211+5)z
(CI(□)zctl(COOtlXCHz)z (S
C2114)2CO2H Regarding the synthesis of the above-mentioned sulfur-containing compound, the compound represented by formula [■] is disclosed in JP-A-62-23
No. 035, -Formula CI+) is published in JP-A-63-172266.
No. 63-172267 can be referred to for formula (III).

The gold storage compound may be added during the production or growth stage of silver halide grains, but it is preferable that it be present from the production stage. Also, the amount added is lo-6 to 20moff/AgXwoff based on the final silver halide.
, preferably 10-'-101]IoQ/AgXmo
(There is one.

The emulsion grains in the present invention contain silver halide (A gX ).
A structure in which guest AgX is distributed as a complete solid solution phase within the particle throughout the particle or partially with a uniform or continuous concentration gradient, or a structure in which guest AgX is distributed within the particle as a solid solution or non-solid solution phase with a discontinuous concentration gradient, This includes a structure in which AgX particles are dispersed in a shell-like manner, and a system in which AgX particles have different AgX compositions between particles, and each particle has the above-mentioned composition distribution within the particle.

Hereinafter, the shape of the AgX particles according to the present invention will be referred to as a mixed crystal.

Furthermore, Ag prepared in the AgX emulsion preparation process according to the present invention
The X grains contain 30 moQ% or more of Ag
o It is preferable that the content is Q% or more. Further, when the light-sensitive material has a multilayer structure, it is preferable that the emulsion layer is selectively applied to at least the emulsion layer in which the effects of the present invention can be most utilized, or that the emulsion layer is applied to all the layers.

Next, the AgX emulsion preparation process according to the present invention will be explained.

In the present invention, the main elements for preparing the mixed crystal AgX emulsion are:
Ag with the smallest solubility product among the mixed crystal AgX components!
A supplied to form and arrange fine grains (in the present invention, they are similar to latent Ag1 grains), seed emulsion, and mixed crystal grains.
There are three gX growth factors (referred to as supplementary AgX factors).

The supplementary AgX elements are soluble silver salts (numerically silver nitrate) and soluble halide solutions as well as fine AgX particles.

In the emulsion preparation process according to the present invention, seed emulsion grains are added prior to the addition of supplementary AgX elements in a suspension system (referred to as mother liquor) that serves as a preparation site in which mixed crystal AgX grains are formed and arranged. Although in the mother liquor, the latent AgI particles are at the latest replenishing AgX
It is sufficient if it is present in the mother liquor until the addition of the elements is completed, but it is preferable to add it at a position where it forms an intermediate shell layer of the particles. Therefore, it may be present in the mother liquor prior to the seed emulsion. Further, the supplementary AgX element may be added intermittently or in multiple stages during particle generation or growth, continuously, or all at once.

Even in the case of a silver iodobromide mixed crystal with a considerably high silver iodide content in the final composition, it is preferable that the total AgH1k is covered by latent Ag+ particles, but it is preferable to supply A to the AgX element within a range that does not impair performance.
The amount of gl produced may also be included.

If latent Agl is present in the mother liquor prior to the seed emulsion grains, Kl, AgN0. may be used to generate Agl in the mother liquor. Of course, separately produced latent Ag1 particles may be added to the mother liquor.

The step of growing seed emulsion grains with supplementary AgX elements is performed using known methods for preparing monodisperse emulsions, such as JP-A-54-4852.
It is carried out by the method described in No. 1. In the present invention, the supplementary AgX element may be added in multiple stages. Further, at least the supplementary AgX element addition is performed in the presence of Kinzo AgX solvent.

In the step, the temperature of the mother liquor is 10 to 70°C, preferably 20 to 60°C, and 9Ag is 6 to 11, preferably 7.5
~1O15, pH is 5-11, preferably 7-IO.

When preparing AgX emulsion (including when preparing seed emulsion),
Substances other than gelatin that have adsorption properties on particles may be added. Such adsorbing substances are useful, for example, compounds or heavy metal ions used in the art as sensitizing dyes, antifoggants or stabilizers. Specific examples of the above-mentioned adsorptive substances are described in JP-A-62-7040.

Among the adsorbent substances, it is preferable to add at least one of an antifoggant and a stabilizer at the time of preparing the seed emulsion in order to reduce fog and improve stability over time of the emulsion.

Among the antifoggants and stabilizers, heterocyclic mercapto compounds and/or azaindene compounds are particularly preferred. Specific examples of more preferred heterocyclic mercapto compounds and azaindene compounds are described in detail in JP-A-63-41848, which can be used.

The amount of the heterocyclic mercapto compound and azaindene compound added is not limited, but is preferably 1X10-' to 3XIO-' and more preferably 5X1 per mole of AgX.
0-' to 3X 10-' moles. This amount is appropriately selected depending on the manufacturing conditions of the AgX particles, the average particle size of the AgX particles, and the type of the above compound.

For finished emulsions with specified grain conditions, Ag
After the X particles are formed, they are desalted by a known method. As a desalting method, Japanese Patent Application No. 62-81373 and No. 63-9047
The agglomerated gelatin agent used for desalting AgX particles as seed particles described in the above issue may be used, or the Zudel water washing method in which gelatin is gelatinized may be used, or inorganic salts made of polyvalent anions may be used. For example, a coagulation method using sodium sulfate, an anionic surfactant, or an anionic polymer (eg, polystyrene sulfonic acid) may be used.

The AgX particles thus desalted are redispersed in gelatin to prepare an AgX emulsion.

The composition of the AgX grains is not particularly limited, and silver chloride, silver bromide, and silver iodide can be used in a composition ratio suitable for gold. A
Although the composition of gX may be a uniform composition or a shell layer type core/shell structure, the preparation method using latent Ag+ according to the present invention is effective for a core/shell structure.

The average particle size of the AgX particles is not particularly limited and may vary depending on the application, but is preferably 0.1 to 3.0 μm. If the average particle here is a cubic AgX particle,
In the case of a shape other than a cube, the side length is the length of one side when converted to a cube with the same volume, and the individual particle size in this sense is ri, and the measured particle size is When the total number is n, the average particle diameter 7 is expressed as Σri r ;. n The monodispersity used in the present invention generally has a value (coefficient of variation) of 0.20, which is the standard deviation σ of the particle size distribution divided by the average particle size 7.
It is said about the following particle groups.

The emulsion according to the present invention is chemically sensitized by a conventional method. Namely, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, reduction sensitization using a reducing substance, and metallization using gold or other noble metal compounds. Sensitization methods and the like can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizer can be used as a chemical sensitizer, and sulfur sensitizers and selenium sensitizers are particularly preferred.

Examples of sulfur sensitizers include thiosulfates and allylthiosulfates.
rubazide, thiourea, allyl inthiocyanate, cystine, p-toluenethiosulfonate.

Examples include rhodanine. Others, U.S. Patent 1.574
．． No. 944, No. 2,410,689, No. 2,278,
No. 947, No. 2,728.668, No. 3,501,3
No. 13, No. 3,656.955, West German Application Publication (OL
S) No. 1,422,869, Japanese Patent Application Laid-Open No. 1983-2493
Sulfur sensitizers described in No. 7, No. 55-45016, etc. can also be used.

The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, and the size of silver halide grains, but as a rough guide, it is
-7 molar to lo-1 molar culmities are preferred.

Examples of selenium sensitizers include aliphatic inselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenophosphates, diethylselenide, diethylselenide, etc. selenides can be used, specific examples of which can be found in U.S. Patent No. 1,574.9.
No. 44, No. 1.602゜592, No. 1,623,49
It is stated in No. 9.

Furthermore, reduction sensitization can also be used together. Examples of the reducing agent include stannous chloride, diourea, hydrazine, and polyamine.

Further, noble metal compounds other than the total, such as palladium compounds, etc. can also be used in combination.

It is preferable that the AgX particles according to the present invention contain a gold compound. As the gold compound preferably used in the present invention, the oxidation number of gold may be +1 or +3, and various types of gold compounds are used. Typical examples include chloroaurate, potassium chloroaurate, auric trichloride,
Potassium auric thiocyanate, potassium iodoaurate, tetracyano auric azide, ammonium aurothionanate, pyridyl trichlorogold.

Examples include gold sulfide and gold selenide.

The gold compound may be used to sensitize the AgX particles, or may be used so as not to substantially contribute to sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guideline, it is from lo-1 mol to 10-1 mol, preferably from lo-7 mol to 10-2 mol, per mol of silver halide. The timing of addition of these compounds may be during AgX particle formation, during physical ripening, during chemical ripening, or at any step after the completion of chemical ripening.

The emulsion according to the present invention is spectrally sensitized to a desired wavelength range using a sensitizing dye. Sensitizing dyes may be used alone, but
Two or more types may be combined.

A dye that does not itself have a spectral sensitizing effect together with a sensitizing dye, or a compound that does not substantially absorb visible light,
A supersensitizer that enhances the sensitizing effect of the sensitizing dye may be included in the emulsion.

The AgX photosensitive material prepared by the method described above has high sensitivity, good sensitivity preservation, and less fog.

The AgX emulsion according to the present invention can be used in black and white silver halide photographic materials (e.g., X-ray, lithium-type photosensitive materials, black and white photographic negative films, etc.) and color photographic materials (e.g., color negative films, color reversal films, color vapors, etc.). Can be used.

Additionally, photosensitive materials for diffusion transfer (e.g. color diffusion transfer elements,
silver salt diffusion transfer element), heat-developable photosensitive material (black and white, color)
It can also be used for

In the case of multicolor AgX light-sensitive materials, in order to perform subtractive color reproduction, an AgX emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually formed on a support. It has a structure in which layers are laminated in an appropriate number and order of layers, but the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

The AgX photosensitive material of the present invention includes an antifoggant, a hardening agent,
Additives such as plasticizers, latexes, surfactants, color antifoggants, capping agents, lubricants, and antistatic agents can be used as desired.

Furthermore, the AgX photosensitive material of the present invention can be used to form images by performing various black-and-white development treatments or color development treatments.

Color developing agents used in color development processing include aminophenol and p-phinidine diamine derivatives that are widely used in a variety of color photographic processes.

In the color development process of the AgX light-sensitive material of the present invention, after the color development process, a bleaching process and a fixing process are performed. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Furthermore, stabilization treatment may be performed in place of water washing treatment, or both may be used in combination.

〔Example〕

Next, the present invention will be explained by examples.

Example 1 (Preparation of seed crystals) The following solutions were prepared.

Solution A Potassium bromide gelatin Solution D Potassium bromide solution Potassium iodide gelatin 0.2N Sulfuric acid Solution C Potassium bromide solution Potassium iodide gelatin Solution D Water 3Q 4.1g 0.2kg 5.2Q 30g 3.6g 10g 7cc Q 1.90kg 4g 50g 5.40 Silver nitrate 190gE liquid water
6.4Q silver nitrate 2.
Solution A was placed in an 82 kg reaction vessel and kept at 60°C, and the other solutions were added at 59°C. At this time, liquids D and D were added over a period of 30 minutes using a controlled double jet method, and then liquids C and E were added over a period of 105 minutes using a controlled double jet method. Stirring is 800r
I went with pn+. The flow rate increases in proportion to the total surface area of the silver halide grains as the grains grow, so that new growth nuclei are not generated when the additive solution flows in, and so-called Ostwald ripening occurs, resulting in a change in grain size distribution. It was added at a flow rate that did not spread. When adding silver ion solution and halide ion solution, pAg was 8.3±0 using potassium bromide solution.
．． 05, and pl+ was adjusted to 2.0±0.1 using sulfuric acid.
Adjusted to. The obtained emulsion had a silver iodide content of 2 mol%, a grain size of 030 μm, and a ratio of σ/γ−0.11, (111)
The particles were monodispersed 14-sided tetradecahedral particles with slightly rounded corners and 5% of the particles were 100-sided.

After seed crystal growth, pn was adjusted to 6.0 using sodium carbonate solution.
After adjusting the temperature to 0 ± 0.3, the temperature was lowered to 40°C, and desalination was performed by a coagulation method using naphthalene sulfonate formalin m fat water a i and magnesium sulfate solution, and gelatin was further added. In addition, pAg-8,50, pH
16.9 kgf of seed crystal emulsion (A) having a particle size of 5.85 was obtained.

The obtained seed crystals were cooled and stored in a cool dark place.

Next, particles were grown using the seed crystal (A) in the following manner.

(2) Preparation of comparative emulsion Em-l First, the following solution was prepared. All amounts/) are given per mole of silver halide.

Solution J (reaction mother liquor) Gelatin 10g Concentrated ammonia water 28cc Glacial acetic acid 3cc Water To make up to 600cc Liquid potassium bromide 5g Potassium iodide 3g Gelatin 0.8g Water E to make up to 110cc Potassium bromide 90g Gelatin 2.0g Water To make 240cc Finishing M liquid (
0.75N) AgN0. 9.9gNl1. Ol(
7.0°.

Water Finishing to 110cc E liquid AgNO3-130g NI+4011 100cc water
0-liquid potassium bromide to be finished to 240 cc 94 g Water E solution to be made to 165 cc AgNO 39.9 g NH,OH 7.0 cc Water To make to 110 cc Solution J was kept warm at 40°C and stirred at 800 rpm with a stirrer. The pH of Solution J was adjusted to 9.90 using acetic acid, and 6.2 g/1 mole of AgX of seed crystals (A) were collected and dispersed and suspended therein. Thereafter, P solution was added at a constant rate over 7 minutes to bring the pAg to 7.3. Furthermore, add 20% of K solution and M solution at the same time.
It was added over a period of minutes. At this time, pAg was kept constant at 7.30 (Step 1). Further, using potassium bromide solution and acetic acid over 10 minutes, pl+=8.83, pAg=9
．． After adjusting to 0, N solution and L solution were added simultaneously over 30 minutes. At this time, the inflow velocity ratio at the start of addition and at the end of addition was 1:10, and the flow velocity was increased with time. In addition, pi was changed from 8.83 to 8.83 in proportion to the inflow amount. OO
It was lowered to Also, L liquid and N liquid account for 2/3 of the total.
When the amount was added, additional liquid 0 was injected and added at a constant rate over 8 minutes. At this time, the pkg ranged from 9.0 to 11.
It rose to 0 (Step 2).

Further acetic acid was added to adjust the pH to 6.0. Next, excess salt was removed from this suspension by the desalting method shown below to obtain an emulsion. While keeping the suspension at 40°C, add the following compound I (5g/AgX a+*Q"), Mg
5O* (8g/AgX 1 moQ) was added, stirred for 5 minutes, and left to stand. Next, drain the supernatant and add AgX
The liquid volume was set to 200 cc per mo12. After that, 40
Pure water (1,81/AgX 1 trhoQ) at °C was added and stirred for 5 minutes. Next, Mg5o, (20g/
AgX1 mob) was added, stirred in the same manner as above, allowed to stand, and the supernatant was removed to perform desalting. Next, post-gelatin was added to redisperse the AgX aggregates, and the mixture was stirred at 55°C for 20 minutes to obtain comparative emulsion Em-1.

(2) Preparation of comparative emulsion E+n-2 The following solution was prepared. All amounts are silver halide 1
The amount is given per mole.

Q solution Potassium bromide 5.0 g Gelatin 0.8 g Water R solution Kl to be finished to 110 cc Water 3.0 g Water To finish to 40 cc In step 1 of the preparation of comparative emulsion Em -1, after adjusting the pAg to 73, rush the R solution. Added with. After that, K.
Em-2 was prepared in the same manner as Em-] except that Liquid Q was used instead of Liquid.

■ Preparation of comparative emulsion Em-3 (Preparation of Ag + fine grains) S liquid gelatin 42 g K1 9 g Na citrate 3 g Water T liquid silver nitrate to finish to 110 cc Water U liquid Kl to finish to 250 cc 147 g Water M liquid silver nitrate to finish to 250 cc Water 28 cc Put the S solution into the reaction vessel and keep the pAg at -13.0, and add the T solution and UliN.
The mixture was added over a period of 30 minutes using the WoControl Double Diet 1 method. Thereafter, liquid M was added in a rush to prepare AgQ fine particles. The average particle size of these particles is 0.07 μm
Met.

Next, the following solution was prepared.

W liquid silver nitrate 6.9 g Ammonia 7.0 cc Water 110 cc In the same manner as in step 1 of preparing comparative emulsion Em-1, pAg=7.
After adjusting to 3 and adding the above Ad fine particles in a rush,
A layer containing 35 moffi% silver iodide was formed using liquid W and liquid Q. Other than that, use Em-3 in the same way as E+a-1.
was prepared.

■ Preparation of Comparative Emulsion E+a-4 In the above step 1 of Em-3, the Agff fine particles were added at a constant speed while adding the W solution and the Q solution.
Ea+-4 was prepared in the same manner as Em-3.

■ Preparation of comparative emulsion Em-5 first,
Compound S-2 and Em according to the present invention were added to the X solution kept at 60°C.
-1 and the same amount of seed crystals (A) were included, and the pH was adjusted to 6.0. Using this liquid as a mother liquid, Y liquid and R liquid were added over 20 minutes using the double jet method, and the silver iodide content was 35soQ.
% silver iodobromide layer was formed. (Step 3) Next, Z solution and L solution were added simultaneously over 30 minutes to grow to 90% of the grain size. During this time, p14=6, (1, pAg-7,
3 (Step 4), then the O liquid was controlled to 8 with the nozzle.
Additional addition was made in portions to reduce the pAg to -9.5, and 3 minutes after the addition of the O solution was completed, the mixing of the Z solution and the L solution was completed. The obtained suspension was desalted in the same manner as Em-1 to obtain Em-5.

■ Preparation of emulsion EI11-6 of the present invention N liquid Potassium bromide 12 g Gelatin 0.8 g Water In step 3 of the preparation of comparative emulsion Em-5, which is finished to 207 cc, Y liquid containing 5.7% of the silver used in the preparation was added. After the addition, the R solution was added in a run, and then the remainder of the Y solution and the rI solution were simultaneously added over 20 minutes to form a layer containing 35 moQ% silver iodide. Em6 was otherwise prepared in the same manner as Em-5.

■ Preparation comparison of emulsion Em-7 of the present invention In step 3 of preparing emulsion En-5, liquid Y and liquid R are added at the same time for 20 minutes, but at the same time as the addition of liquid Y and r1 starts, as described in Em-3. Em-7 was prepared in the same manner as Em-5, except that 0.07 μm AgQ fine particles were added in a rush.

■ Preparation of emulsion Era-8 of the present invention In step 3 of the preparation of comparative emulsion Em-5, liquid Y and liquid R were simultaneously added for 20 minutes, and the Agff
Em except that the fine particles were added at a constant rate during the mixing time.
Em-8 was prepared in the same manner as Em-5.

Further, emulsions Em-9 to Em-16 were prepared using methods ① to ② and by changing the combined AgX solvent according to the present invention.

Table 1 shows the particle preparation method and the type of Kinzo AgX solvent. All of these emulsions had monodisperse grains with an average grain size of 0.60 μl and a silver iodide content of about 2 mof2%.

Next, the obtained particles were chemically sensitized. That is, 50m
g/AgX I Iloα of ammonium thiocyanate and 6 mg/AgX I moQ of chloroauric acid and 35 m
g/AgX 1 mo (+ hypo) was added and gold-sulfur sensitization was performed at 55°C.

Then, 1.5 g/AgX 1 moff of 4-hydroxy-6methyl-1.3,3a,7-titrazaindene was added, followed by 150 mg/8 g 300mg, 5mg
/AgX l moQ was added to perform spectral sensitization.

Next, a coating solution for the emulsion layer and a coating solution for the protective layer containing the obtained emulsion are simultaneously coated in two layers on both sides of the subbed polyester film support in the order of the emulsion layer and the protective layer from the support side. After that, it was dried to produce a silver halide photographic film.

The following additives were added to the emulsion layer per gX1 mo (l).

[-Butylcatechol 400mg
Polyvinylpyrrolidone 10g Trimethylolpropane 10g Diethylene glycol 5g Nitrophenylphosphonium chloride 50+ng 1.3-Dihydroxybenzene-4= Ammonium sulfonate 4g 2-Mercagutobenzimidazole-5CsF+s OiC
HtCHtOh1CH□C11□0112mg CHs So 3 H C,F, 3mg for □S03 1.1-dimethylol-1-bromo-1-nitromethane l10ff1 Styrene-maleic anhydride copolymer 7.5g In addition, gelatin was added to the protective layer. For Ig, the following compounds were added.

CH! Coo(CHt)s CHsSo, Na 0-(C112C020 juice ■ Polymethyl methacrylate (matting agent) with average particle size of 5 μm 7 mg colloidal silica (average particle size of 0.01 μl) 70
mg(CIIO)z aqueous solution (40%)
1.5+mQHCIIO (35%)
2m (2 subtracting liquids include glycidyl methacrylate 5Qvt%, methyl methacrylate
A copolymer consisting of three monomers: 10vt%, butyl methacrylate 40vt%, the concentration of which is 10wt%.
An aqueous copolymer solution was used after diluting it to %.

The samples thus obtained are shown in Table 1.

Also, the amount of gelatin in the unexposed film of this sample was 3.5 mm per side. It was lOg/m2.

[Sensitometry]

Using the standard light B described in "New Edition, Lighting Data Book" as a light source, the film was exposed to light with an exposure time of 0.1 seconds at 3.2 cm5 without a filter so that the same amount of light was applied to both sides of the film. The above sample was processed with XD-3R developer for 45 seconds using a 5RX-501 automatic processor (manufactured by Konica Corporation).
The sensitivity of each sample was determined. Sensitivity is determined by calculating the reciprocal of the amount of light required for the blackening density to increase by 1.0, and
It is expressed as a relative sensitivity with the sensitivity of t as 100.

[Storability test]

Regarding the obtained sample, under the conditions of 80% Rb and 40 ° C.
A sample stored for 3 days and a sample stored for 3 days under conditions of 55% Rh and 23°C were prepared, and the above-mentioned sensitometry was performed.

Table 1 shows the sensitivity at 55% RH and 23°C as 100
The sensitivity at 80% and 40°C is shown as relative sensitivity.

Example 2 (1) Preparation of emulsion Ea+-17 An aqueous solution of 112 (pBrl.

70, p12.52) was maintained at 70°C, and 50 ml (l) of 4 N AgN0z was added at constant speed over 1 minute 15 seconds while stirring well. During this time, pBr was increased to 1.
4 N while controlling it with a silver electrode to keep it at 70.
KBr was added at the same time. Then 2N AgNOx solution and 2N KBr.

A mixed solution of 0.04N KEr and Kl was added to 10
The simultaneous additions were made over a period of minutes. However, the addition rate of 2N AgNOs is 6m+2/win, and the final amount is 74mQ/win.
It was min. During this period, the amount of 2N AgNo added was 400 m+2, and the pBr was maintained at 1.85. Two minutes after the end of this addition, the temperature was lowered and washed with water, and then 120 g of inert gelatin was added to make the volume of the emulsion 200 nu2, and the pAg at 40°C was 9.1. p) After adjusting l to 6.9, the temperature of the emulsion was raised to 60°C and lmM of 5
-Benzylidene-3-ethylrhodanine 18+i (2° chloroauric acid 4.4 mg, potassium thionanate 135 mg
was added to perform chemical sensitization for 60 minutes. Then, Kl and sensitizing dyes ■ and ■ were added in the same manner as in Example 1, and E
ta, -17 was obtained.

■ Preparation of Emulsion E+a-18 1 After adding 3111IIloQ of AgNOU solution to an aqueous solution containing 15 g of inert gelatin, add 3111IIloQ of Kl aqueous solution.
Add flOQ. Next, 20 mg + oQ of AgN
0. solution and an equimolar aqueous KBr solution were added. Then, while keeping pBr at 1.70, 4N AgN0. The aqueous solution and 4N KBr solution were added simultaneously. Then emulsion Em
Em-18 was prepared in the same manner as Em-17.

■ Preparation of Emulsion Em-19 In the method for preparing Emulsion Em-17, 0.05 μm of A was added instead of adding 13 mmol to the mother liquor.
GL microparticles of 3IllIIIoQ were rush added.

Em-19 was prepared in the same manner as Em-17 except for the above.

(2) Preparation of emulsion E+5-20 In the preparation method of Em-17, 4N and AgN0. While adding the solution, 0.05 μl of Agl microparticles were added simultaneously. Everything else is EI! + -19 was prepared in the same way.

In addition, the compounds of the present invention shown in Table 2 were added to the mother liquor, and the
Prepare Em-21-Em-32 according to the preparation method.

A sample was prepared using the sample obtained as described above in the same manner as in Example 1, and the same test as in Example 1 was conducted. The results are shown in Table-2.

As can be seen from Table 11 and Table 2, the sensitivity is the relative sensitivity with the sensitivity of No. 17 set as 100, and it can be seen that the samples of the present invention have excellent storage stability under high temperature and high humidity.

A breakthrough was achieved in eliminating defects in monodisperse emulsions containing spectral sensitizing dyes, and the object of the present invention was achieved. Moreover, from the perspective of crystal growth theory, it has been understood that the crystal system has a small solubility product and not very fine Agl crystal particles are incorporated as guest components in AgX particles, and a new perspective on crystal growth has been gained.

Spectral sensitizing dye■

Claims (1)

[Claims] It has an emulsion layer containing at least one photosensitive silver halide grain on a support, the grain grows in the presence of a silver halide solvent which is a sulfur-containing compound, and the silver iodide grains are redispersed. 1. A silver halide photosensitive material comprising silver halide grains containing silver iodide and incorporated into the grains.