JPS5945438A - Silver halide emulsion and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a monodispersion emulsion of photosensitive silver halide grains each having definite crystalline form and a remarkably narrow grain size distribution, by adding a process for continuously changing a ratio of amts. of >=2 kinds of halide ions to be added with the lapse of time. CONSTITUTION:The silver halide photographic emulsion is prepared by mixing silver halide ions with halide ions in the presence of a protective colloid by the double jet method, while maintaining pAg constant, and at that time, halide ions are composed of >=2 kinds selected from chloride, bromide, and iodide ions, and a ratio of amts. of >=2 kinds of halide ions to be added is continuously changed with the lapse of time in a process included in the total processes. As a result, the obtained monodispersion emulsion is composed of silver halide crystals continuously changing in proportion of the silver chloride and bromide of a part or the whole crystals, and of photosensitive silver halide having a remarkably narrow grain diameter distribution.

Description

DETAILED DESCRIPTION OF THE INVENTION Invention C", crystal σ)-1 or all 1.iX silver oxide and silver bromide compositions are continuous, -r change I2. It is composed of silver halide crystals with a certain cedar-like shape, and the size distribution is significantly narrower than that of photosensitive silver halide. (/'l ll'j 't) Number sequence? i'l
ノRJ 'fJ＞ Method cy 類'lるf) No C.

Silver halide sensitive material:, i6, IT, 1
．． Stretchability, sensitivity, τ1:, 7. of Trust Lab. −、! ′
(Characteristics) Large shadow VνA due to silver halide composition 17%
・Uke 4. do. However, the silver halide composition 1 is controlled in order to obtain the desired photographic properties, but by setting a specific halogen composition, it is possible to obtain the desired properties.
IJ+, where small necessary characteristics are given, warehouses are often placed, and the desired 77'true characteristic 1'/1. ing. Part 1
(,-Surface and interior of silver halide crystal)・Rogge 7・
There is a way to change Kaga # and II formation.

This method is 'q direct'4'! It seems to be effective at -1- to control j properties: 1-4, but in order to bring out the effect, 0.
]・14 with less variation in silver halide composition, t)'l J'-') size, and shape is the best! Asked for, received. 111i
a) A specific part of the particles is converted into a desired halogenated 414
ii! ++ Requires advanced playing skills.

In general, silver halide grains widely used in the industry and used in real materials, such as silver halide particles,
-"Q) Existence of aqueous halide solution in water" 5
Mixing with stirring and aqueous silver salt solution
, - made as a silver halide emulsion. Examples of such manufacturing technologies include the singel jet method, double jet method, and 7
Methods such as the method are known. Single je.

1. Law? , l: , Anti-Lt, , This is a method of obtaining silver halide crystals by placing an aqueous halide solution in a container and adding an aqueous silver salt solution thereto for a certain addition time while stirring. On the other hand, the Double Sh, T method is the opposite of 1+i;: Container (5 Nigelatin aqueous solution or silver halide 1':
- A silver salt aqueous solution and a halide aqueous solution are simultaneously added at a very specific addition time (G1) to form silver halide crystal grains.

In addition, the sound 1ζ'y in the crystal 7r is specified by the method and 11. for producing silver halide crystals in which the composition ratio of all silver chloride and silver bromide is changed continuously. Kimiaki!”+(1-3
There is a method described in 6978υ. 1. After forming silver chloride or silver chloride microcrystals containing at least 4 parts of a silver salt whose solubility in water is greater than that of silver bromide, easily soluble bromide or bromide and iodine are formed. By adding the aqueous solution of the compound to the emulsion, a) caulking is formed, and the F compound in the silver chloride or silver chlorobromide microcrystals is formed. 4) The difference in the solubility product of the silver salt is utilized. Then, chloride (A) is converted into IF7 with bromide and/or iodide. This is the way to obtain.

In this method, the bromide ions and/or iodide ions added later convert the chloride ions already present in the crystals, thereby changing the grain size of the crystals (chemistry 5, lt).
NO) does not change, but the crystal surface GJ silver iodide compared to the inside of the crystal forms a crystalline phase with a high content of silver iodide. and/or G' iodide ions and equimolar ion chloride in solution &J
released.

l-σ) The emulsion formed by the yonaconversion method Gj- has the property of desensitizing the emulsion to pressure G. This property is subject to photographic fees)'? ',,Currently, when pressure is applied at the statue's culm,
IT - The part where the force is applied is white, which is a waste of time for a product.1゜kneading is a product with a white color because crystal seeds are produced during the nitrogen conversion reaction (J"-7J). ”!It is estimated that this will happen.

In addition, the convergence method uses silver halide σ) solubility 7.
Published by J[Eye, the mole percent of silver chloride on the front side of the crystal was increased!・711 to produce tJ silver gemide crystals? ;
W) in 1 hour.

Therefore, the L1 purpose of the present invention is =l synversion method? i)
It is an object of the present invention to provide a silver herolanide V true emulsion and a method for producing the same, which are improved from the disadvantages of silver 1genide true emulsions. In other words, is there a conversion method that eliminates the above defects? without disturbing the crystal seeds r・yJS′/, “<
, one 7'lt (also G' all j'
'1R J'lA silver oxide and embodiment (14 introduction 7J- Ratio changes continuously ζ゛ 1 Genide flI! made of crystals,
The individual crystals have a certain shape, and the diameter is extremely narrow.
111 minute Vit emulsion and its manufacturing method are provided.

The first object of the present invention (from the description of the specification) is 4C.

June of the present invention - 1l'l<J 11 , qj ko I
+ - (Tono existence i [-bottom, l') Ag3-・shi1! G.
- Ri(, 勺"-) Duffalgiat method G1-" Nili(?
By adding IJ ion and halogenated 1'1' halogenated E++ crystal, make IJ 11 genated IR.
l'/;: )'<Production method of emulsion i;=,+;, and the halide -(A is a chloride ion, !11ft
; t selected from Q2r and −r compounds;
J rikuno゛L-+ 2 i'ij(kara l'li sei 2
Zawa 2, and Hl /J,> (2) A method for preparing a silver halide emulsion containing 4 culms, and a silver halide emulsion produced by the method.

Look, the X monster is here! The method of adding 2 or 3 types of Δylene compound and nonatide ion is particularly important for IL!
It may be added directly to the mother liquor to form an emulsion separately, or the mother liquor may be added directly to the mother liquor after pre-mixing.
C is also good.

It is advantageous that the silver halide to be used in the present invention has an iodide content of 1 to 2 mol% or less, an oxidation ratio of 50 to 97 mol%, and a balance of silver chloride. rt7:
, aL, (Characteristics [・Emulsion preparation: 3() to 70°C, 1]-
The range of Ag4 to Ag9 is preferable. In addition, ・Two places r p
"1" while keeping Ag constant means that the pAg value is controlled relative to the set value.

In a preferred embodiment of the present invention, silver iodide and halide ions are mixed without addition, and silver iodide is a mol %, silver chloride is b mol %, and iodide, I is Cq. Nil%
When silver halide is raw Y1 or 1 for 2 minutes, a>0,
b) 0. c (l) a4-h 0c = 10 (1, and the molar ratio of the embodiment of the halide ion: chloride ion: iodide ion is a: kb: c (however) ■7.1\k ::>= (1°9), the silver (
71 wo supply), -me (ha melt t1 da (first solution)
, and a filler for supplying halides (11) and halides (11). iV (second solution) σ) outside r! , and ■! 1 (Chemide-I→N4・Using the old fifth solution, silver I4・) Concentration ',' R1! 49 stone j l, -) 7) Halogenation (?14', -iH; ”5 (：Jruj
ij! Sama)) ζageC) Neru.

,'-(1) Implementation FiM, f'+', h, J, i(
, 1. The correct solution IC da σ) In the chloride, -Jn and -1, In the L chloride, the ratio of ]n (T-R ratio) is within the range shown by )' in the formula 1. There is (-Togasara G Kokoi: J5 Shii.

Y--1<X I・In the formula, K 114 (1 to +2 (11-number of 10,
ill /J' Ien＼(jruha11genification(il
lJ, C1/Tl (mol J17).

The feed rate of the halide r)l is continuously
1-ri(formation i]ru1, (: l-1, e.g. place'/i
! Added TO− chloride ion solution, Jil (l'1 clause r・) ion solution and iodide ion solution t1) 3: □ Separately prepare 11, each solution σ) Between zero and i!speed i' based on the silver halide composition ratio
li#'"), the song number, and the -change tJ.

For controlling continuous changes, various means commonly used for flow rate control can be used.

In addition to the photosensitive characteristics of silver halide emulsions,
The necessity of controlling pAg and its control during production with respect to crystal habit, particle size distribution, silver halide composition fluctuations, etc., can be understood from the following documents and patents.

That is, Journal of PhOlog
rapic 5science) Volume 12 P, 242~
251 (1,964), Volume 27, P, 47-53
(+979) G, j This shows that the crystal habit and shape of silver halide depend on the pAg at the time of production.

In this way, the difference in the chemical ripening characteristics of the silver halide I and the agent L'CG,t
Ji.

-1-Noru Kabu Photography, Reliance (
Journal of Photographic 5
science) Volume 14, P, 1B+, -184
(1966) and many other reports, l'j d'
What is the pAg of t II,',r? It is closely related to the photographic properties of the emulsion.

Journal of Photography, Reliance (Jourr+al of Photography
c 3science )@'! Volume 27, ■), 1-12
(1979) show that the solubility of silver halide is dependent on pAg. T'tulI
rLin Of tl+eSnrir+y of 5
scientific photography of
, J, +pan) No. 16. '! e Xl,', l
□ Many reports, including 7 (1966), state that the Iq of silver halide is σ) Pl of silver halide.
'l' I (indicates that it is 1-proportional to l. These documents are 1'') is also har, + flt of the Genka year emulsion! I
In 'lti, pAg determines the growth rate of silver halide)ffi? L, (- and +w angle γ are formed.

Mar, -Special 111TII l((5!'l-I 436
7 So detailed if ni? ;) Iodized silk with high content 'fr%i 6゛・containing iodine r;I ηi+1 each'? G1. i-
; Then, if the pAg at the time of f-refilling is halogen housing 11L) and the grain size is one throw, the shadow will not be affected.
There is no indication that there is more.

I--Details G,--As mentioned above, control of pAg using the red double gel method and method of emulsion production]'1,1. i'1.5-i1,t Z+
1' Me c self must be 9! In the present invention, pAg's huntry-/l//! is the monkey condition. −、
J′ri strict k.

Purpose of use 6. Divide m and E into two parts 7, and use one of the liquids (hereinafter referred to as the second double 31) to add the silver ion solution (hereinafter referred to as the first solution) per hour. [1 Add approximately the same molar amount of silver halide to the silver solution (2) Add silver halide (1) to the river, add I7 to the other liquid (
Addition of the first and second solutions (hereinafter referred to as the first solution) 6)
It is preferable to add chloride ions and bromide ions so that the change in pAg is equal to the change in pAg (and the change in pAg is sufficiently small), and to provide for the control of pAg.

History G, - Photosensitive silver halide crystal at each time point &Jl/1. The composition of silver halide to be formed is silver y oxide; 1 mol%
, Ht eJJb mol%, when iodide eH is 0 mol% (
Here, a and l) are positive numbers, C 0 or positive numbers 1. :l
-1-1) -1-c-100), each uJ? At the point Φ, from the two solutions, the molar ratio is 1≦qJj, a pair (+ ~
(1,9) b71Ci7) Proportion σ) Furnace compound,
Addition of chloride ion and iodide at t7, and by using the third solution, r=11 chloride ion and bromide ikarne are added to γ1. 6J of agent was added! 71. It is preferable to maintain the agent at a predetermined pAgk and control the halogen composition ratio of the silver halide produced by the first solution and the second solution. There is also the effect that the desired silver halide composition is stable (J: , 1: <?!j et al. 1, ma 1.).

Y −= K (b / R) where 1×ζ
, 1.40e-~120(l positive number, Y(21 AA solution ゛C added λl('17Br-ratio(1000tx,
l't,) to L(・).

The value of G1-1I is determined to be within the range determined by the following formula: , L is preferable.

■ku -:・ (()34゜ !1 -- 12.
751 + (1, n793812) S here τ
",' CJ hal+genation f'N A-generation 1..I
M ff1l-a emulsion fiJ solution i'! i1'+I
α (to “), S Il, 3~ノ, ′A with a positive number of i;
Ru.

(Record fp: ゛, solution core, 1, single ((halogenide extraction per hour σ) addition [11 or addition of silver extraction by the first solution iHi to ii Tri' +! 7 L, <
I, r Z+ J: 'J ni(' (/,) il
,l! What is the GJ addition rate? , it is only necessary that the IN settings are completed. The amount of halide added by the third solution (uQi) or the first and second solution (A') or the number of halide added by the second solution (σ)% or more is added: sea urchin concentration 1u1 and/or Preferably, the rate of addition is regulated.

In the present invention, the method of mixing the silver ion solution and the halide ion solution is not limited as long as the purpose of mixing is achieved, but it is preferable that the iK of mixing homogenization is high, that is, the mixing efficiency is high. Poor mixing efficiency! ? In terms of R, the rise and fall of pAg is 1. This is because it changes the Φ dispersibility and emulsion properties.

Therefore, in the present invention, it is desirable to use the premix method. Taking an example of emulsion preparation, the premix method and C'introduce the inflow of liquids to be mixed, and the factors that influence the mixing efficiency, such as the inflow direction, temperature, and stirring exchange rate, are controlled: iiJ, Mixing volume) The solution that is rapidly circulated and supplied in 4P is 1-2. A silver ion solution and a halide ion solution are injected into the mother liquor of 7I, etc. and immediately mixed and homogenized to produce 21i! This is a method in which the water is released and mixed into the mother liquor outside Kinza.

The mixing agitator used in the premix method is a special M1
1981 No. 1681.93, 1981 No. 168194 and Jurnal Nauzinoi i Prikladnoi Photography i Yoshinematography;? A% volume (19
78), No. 64'#i to No. 75, 100% Ni Nself i1a
Sawa, 'Ci Z+.

A method for producing a silver chloroiodobromide emulsion containing silver and silver of the present invention?
If the temperature is too low, the IQ of the crystallized liquid will decrease, but if the temperature is too high, the water will wilt and be ignored. ζ No to 40・
A cow whose temperature is ~70°C is qslX+.

In addition, the Il and Ag of the emulsion are not determined to be 11tH for erection, but
εjI!・When the f:fl concentration or &:jJytriride concentration is high, the V true characteristics of the copper chlorobromide scrap and chloriodide silver ξide emulsion exhibit favorable and <<4 It is preferable that the value is between 4.0 and 9.0.

III sound force method ζ of the present invention, power force method 1: silver, chloride y
chlorination (also σ with respect to IJ), P), chloride of silver halide ("14, μ chloride Cμ and iodide C[((HaF%0, - is 1114 and 4" silver iodide (taking into account the characteristics of the halogenated ΦN, especially 2 mol% or less σ), 50 to 97 mol% of silver chloride, and a salt with silver chloride C of 50 to 97 mol%. 18■ Made of silver chloride and silver chloride iodobromide 'AIj
G,-apply 7 or c, knee'! 'You can reach your goal at your own advantage.

In the present invention, water-soluble polymers, such as natural or synthetic polymers such as gelatin and polyvinyl alcohol, can be used in combination as a colloid. The total Ji of the time-keeping colloid is the objective halogenated ε1 (particle properties and manufacturing conditions end 1r=
0.5 to about HIJ for solution 11, depending on the
It can be arbitrarily selected within the range of 9.

A typical example of the silver oxide solution used in the present invention is an aqueous silver nitrate solution. Also, 1-1 to 2 moles of silver nitrate
Add more than mol of ammonia and mix with silver ammonia 31 monolithic aqueous solution and 1. It may also be used.

The halide ion A used in the present invention is supplied as a water-soluble halide. As the halide,
Potassium iodide\, sodium iodide\, 1; potassium iodide 8, sulfur bromide 1\, potassium chloride\, potassium chloride\, sodium chloride\, and monium chloride are used. It will be done.

In the present invention, the concentration of the silver ion solution and the halide solution can be arbitrarily selected depending on the purpose and production conditions. Preferably, the depth is 0.5 to 73.0τTIO
It is preferable to use it at a concentration of I:/l.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 A silver chloride seed emulsion with a silver bromide content of 60 mol % was prepared using a solution of 7 (M'J,'l'l) as shown below. .

[Solution 1-A] [Solution 1-It 1 [Solution (f l-C'] [Solution +-T) 1 [71 Inze] Jin 27. ′／〔
Solution 1-E': 1 [Solution? t'tj + --t') [Solution t-
a] 7% carbonic acid → Triuno ＼ water soluble? (Ii 2ns
At 140°C, add solution 1-8 to solution +-yi and solution 1-8 using a mixing stirrer shown in the same specification.
When D was added for 29.5 minutes by the double bulge type method,
Added 17 times. Ekaoki 1 (MeO) Shown in Table-1 4, 1-UG, -1 hour] Both 41inePμ] (Me,
It increases with the addition of
For each pull jet method, T8: 1 minute addition time is required, and solution 1-C and solution 1-・E4-addition 1-
.

Ta.

The addition period was increased by 9 days as shown in Table 1. Solution 1-Tl and Solution 1-■), and Solution 1
-C and solution 1-1; between the addition of
Controlled to 0mV)! ,Ta. EAg (1/i measurements are made using a metal silver electrode and a double junction type saturated A1Agc" I
It was measured using a reference electrode. Solution 1-B1 Solution 1-c
1 solution] -J), solution 1-E and solution 1-F were added using a variable flow rate type roller 3-p metering pump. 3 minutes after the addition of solution 1-(' and solution 1-E is completed, the EAg value 'k is
-4-70rnVj, 7p, +114 adjusted.

Washing with water and removal of size were performed by V (J:, J, l・σ) operation A4.

Amor N made by Toshihide Hana - γ Torasne]
17. Add 650ml of 5% aqueous solution and 650ml of 20% aqueous solution (111) to form a precipitate.
1, decant the clear liquid, and then distill it 7 (l Q Ome
5t11t is again distributed -1. 20%l! Acid magosiuno ＼ water solution bay 200771/' 4Z like' 2f 4 and the precipitate was made into a cow. Precipitate settled 1, P 1.1: Decanted the water and added 500ml of an aqueous solution of
/! (4-r containing Oseinbira, Jin50!?) was added and dispersed by beating at 55°C for 30 minutes, and the total hI was adjusted to 2500+n/ with distilled water. Hereinafter, σ) The emulsion should be 11>M-11. Electron microscopy G,
-Therefore, (71. machining of (-) has a side length of (1,14/Iμn
The egg weight deviation of the Ren j〇-distribution is 6'3% of the average particle size from the hemicuboidal particles of 1, which is a high 1CI dispersion agent. Kotowaka 1/, -Table 6-
1 Example 2 The following six types of solutions were used to grow 1'': M = 1 produced in Example 1 as a seed emulsion, and the halide composition was continuously maintained within the grains of the present invention. particle surface i'
1 and Agl-3r 11 monodisperse agents were prepared in which p+n was changed to be high.

[Solution 2-8] [Solution 2-111 [Solution 2-C] [Solution 2-r) 1 [Solution ifl/2-T', 1F [Solution tv 2 apa 5] (i (45 at 1℃) C71=, +7 Gansho 55-Hi81
No. 93, No. 55-'-168194i Using the mixing agitator shown in each specification, solution 2-, A G, -solution 2-
11. Solution 2-(゛ and also as a comparative emulsion 7, Converge □ described in Japanese Patent Publication No. 50-36978 "Zr
An emulsion was prepared using the emulsion method. Below, this emulsion is 1=
; Called M-4.

1 [f, child'j According to the micrograph, J': M -2
, 1-31.5 and EM-4 (percentage of standard deviation of particle size to average particle size) are 6.
．． 7%, 7.1% and 211%, and the present invention (, -
It can be seen that the emulsion according to EM-1 has a dispersibility of 11' and 41', while powder ``Beak's value 1 + J is low, E is 1-2, E M -3 is high 10, intermediate forgiveness.I'1゜ Considering that +'1 quality is uniform between particles 4) It can be seen that the halogen composition has a continuous distribution within the particle.

4. Fl of the drawing: i r)' I na t? (71 Figure 1 (71 Premix Mixing Method 4Y Used in the Present Invention) 4W Stirring Mixing I'j+i Used in Butt7).

Agency included Ngukon Yoshimi

Claims (1)

[Scope of Claims] 0) Addition of silver ions and chlorine chlorides by double jet method while maintaining pAg for a certain period in the presence of captured colloid. Silver chloride emulsion σ to produce silver crystals Production method at least 2
Production of a silver halide emulsion characterized by a process in which the ratio of addition of at least two types of halide ions (h1σ) is continuously changed over time. Method. (2) -, l = - period halide - (continuously changing the ratio of additions of d and 5 over time): each of the normal silver crystals in the culm 1f = The composition W of the silver halide crystals to be produced at the time point is silver bromide a mol%, silver chloride b mol%, silver iodide mol% (however, a + b + c
= 100), use a solution containing chloride ion and bromide ion in the ratio shown by Y in the following formula with the additive solution for controlling pAg, t, -C, A method for producing a silver halide emulsion according to claim 1, characterized in that: Formula Y=K(b/;+) [In the formula, Y 4:t 118g CI A in the control solution
1 r-'f/:j4 degrees (molar ratio), K = 4 (1 to
12 (1 (1)