U.S. patent number 3,839,049 [Application Number 05/275,582] was granted by the patent office on 1974-10-01 for preparation of a silver salt of a fatty acid.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Michael J. Simons.
United States Patent |
3,839,049 |
Simons |
October 1, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
PREPARATION OF A SILVER SALT OF A FATTY ACID
Abstract
A process for preparing a silver salt of a fatty acid in finely
divided form comprising (a) adding an aqueous solution of a
water-soluble noble metal salt to a colloidal dispersion comprising
the ammonium or alkali metal salt of the fatty acid, (b) optionally
adding an acidic solution to the resulting reaction mixture to
convert unreacted ammonium or alkali metal salt to the free fatty
acid, and (c) recovering the noble metal salt of the fatty acid,
provides noble metal salts of fatty acids which can be used in
photographic materials.
Inventors: |
Simons; Michael J. (London,
EN) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
10376686 |
Appl.
No.: |
05/275,582 |
Filed: |
July 27, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Jul 28, 1971 [GB] |
|
|
35344/71 |
|
Current U.S.
Class: |
430/619;
554/74 |
Current CPC
Class: |
G03C
1/49809 (20130101); C07C 51/412 (20130101); C07C
51/412 (20130101); C07C 53/126 (20130101) |
Current International
Class: |
C07C
51/41 (20060101); G03C 1/498 (20060101); G03c
001/02 (); C01g 005/00 () |
Field of
Search: |
;96/67,114.1,114.6
;117/36.7,36.8,36.9 ;260/413 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Smith; Ronald H.
Assistant Examiner: Suro Pico; Alfonso T.
Attorney, Agent or Firm: Knapp; R. E.
Claims
1. A method of preparing a composition comprising photosensitive
silver halide and silver behenate comprising (1) mixing (i) a
preformed photosensitive silver halide emulsion comprising less
than about 30 grams of gelatin per mole of silver halide with (ii)
a fatty acid reactant comprising less than 65 mole percent behenic
acid and 35 to 60 mole percent alkali salt of behenic acid selected
form the group consisting of ammonium and alkali metal salts of
behenic acid to provide a photosensitive silver halide composition,
(2) mixing an aqueous solution of a water soluble silver salt with
the photosensitive silver halide composition to provide a reaction
mixture and (3) adding an acidic solution to the reaction mixture
to convert any unreacted ammonium or
2. A method as in claim 1 also comprising (4) recovering the
resulting
3. A method of preparing a photothermographic composition
comprising (a) mixing an aqueous solution of a water soluble noble
metal salt with a colloidal dispersion comprising a fatty acid
reactant comprising less than 70 mole percent free fatty acid and
at least 30 mole percent ammonium or alkali metal salt of said
fatty acid to provide a reaction mixture, (b) adding an acidic
solution to the reaction mixture to convert any unreacted ammonium
or alkali metal salt to the free fatty acid, (c) recovering the
noble metal salt of the fatty acid and (d) mixing the resulting
noble metal salt of the fatty acid with (i) a preformed
photosensitive
4. A method of preparing a photothermographic composition
comprising (a) mixing an aqueous solution of silver nitrate with a
colloidal dispersion comprising a fatty acid reactant comprising
less than 70 mole percent free fatty acid and at least 30 mole
percent ammonium or alkali metal salt of behenic acid to provide a
reaction mixture, (b) adding an acidic solution to the reaction
mixture to convert unreacted ammonium or alkali metal salt to the
free acid, (c) recovering the noble metal salt of the fatty acid as
a finely divided solid, and (d) mixing said finely divided solid
with preformed photosensitive silver halide, a phenolic reducing
agent and a
5. A method of preparing a finely divided noble metal salt of a
fatty acid comprising (a) mixing (i) an aqueous solution of a
water-soluble noble metal salt with (ii) a colloidal dispersion
comprising photosensitive silver halide and a fatty acid reactant
comprising less than 70 mole percent free fatty acid and at least
30 mole percent ammonium or alkali metal salt of said fatty acid to
provide a photosensitive reaction mixture, (b) adding sufficient
acid solution to the reaction mixture at least partially to convert
unreacted ammonium or alkali metal salt to the free fatty acid and
(c) recovering the resulting product as finely divided
6. A method of preparing a finely divided noble metal salt of a
fatty acid comprising (a) mixing (i) an aqueous solution of a
water-soluble noble metal salt with (ii) a colloidal dispersion
consisting essentially of (1) a photosensitive silver halide
gelatino emulsion containing less than about 30 grams of gelatin
per mole of silver halide in said emulsion, and (2) a fatty acid
reactant comprising less than 70 mole percent free fatty acid and
at least 30 mole percent ammonium or alkali metal salt of said
fatty acid to provide a reaction mixture, (b) adding sufficient
acidic solution to the reaction mixture at least partially to
convert unreacted ammonium or alkali metal salt to the free fatty
acid and (c) recovering the resulting product as finely divided
noble metal salt of fatty acid and photosensitive silver halide.
Description
The present invention relates to the preparation of silver salts of
fatty acids in finely divided form. According to the present
invention there is provided a process for the preparation of a
silver salt of a fatty acid in finely divided form, which comprises
the steps of adding an aqueous solution of a water-soluble silver
salt to a colloidal dispersion comprising the ammonium or an alkali
metal salt of the fatty acid, optionally adding an acidic solution
to the reaction mixture to convert any remaining ammonium or alkali
metal salt to the free fatty acid, and separating the precipitate
containing the silver salt from the reaction mixture. The process
of the present invention provides finely divided silver salts of
fatty acids which are particularly useful for photographic
applications. Further, the process has the advantage that it is
technically simple and uses readily available materials.
Preferably, the colloidal dispersion contains free fatty acid in
admixture with the ammonium or alkali metal salt of the acid.
In a preferred embodiment of the invention, the fatty acid is
behenic acid. In this embodiment of the invention, at least 30 mole
per cent of the behenic acid in the colloidal dispersion should be
present as the ammonium or alkali metal salt. Preferably, from 35
to 60 mole per cent of the behenic acid in the colloidal dispersion
is present as the ammonium or alkali metal salt since such
compositions form colloidal dispersions which are stable at room
temperature. It has been found that extremely good results are
obtained when the composition contains about 50 mole per cent of
the ammonium or alkali metal behenate and about 50 mole per cent of
the free behenic acid. Also, it has been found that colloids
containing less than 40 mole per cent of behenic acid tend to be
relatively unstable at room temperature and therefore may have to
be used at elevated temperatures. The colloidal dispersion is
preferably formed by heating the fatty acid and the aqueous medium
to a temperature above the melting point of the acid but below the
boiling point of the medium and adding a solution of alkali metal
hydroxide or ammonium hydroxide, preferably sodium hydroxide, so as
to at least partially convert the acid to the corresponding salt.
Preferably, the concentration of the fatty acid used is between 50
and 250 grams per liter of aqueous medium although concentrations
outside of this range can be used if desired. Preferably, the
reaction mixture is agitated such as by stirring or shaking to
facilitate the reaction. Where the fatty acid is behenic acid then
the behenic acid and aqueous medium should be heated to at least
80.degree.C. Any water-soluble silver salt may be used to form the
silver salt of the fatty acid but silver nitrate is preferred. If
it is desired to change the relative proportions of fatty acid and
ammonium or alkali metal salt in the colloidal dispersion where it
contains free fatty acid, then the water-soluble silver salt
solution may contain a base, such as ammonia, or the base may be
added simultaneously with the silver salt so as to further
neutralize the acid. This enables a greater amount of the silver
salt of the fatty acid to be formed since it is the ammonium or
alkali metal salt thereof which reacts with the water-soluble
silver salt rather than the free fatty acid. It is possible to
reduce the particle size of the starting colloidal dispersion, by,
for example, subjecting the dispersion to ultrasonic vibration.
This gives a starting material for use in the process of smaller
particle size which reacts more readily with the water-soluble
silver salt.
Where the starting colloid contains free fatty acid then the
precipitate containing the silver salt which is separated from the
reaction mixture will also contain free fatty acid. The product can
be used in this form for photographic applications but if desired
the fatty acid may be removed by treating the product with a
solvent, such as diethyl ether, in which the silver salt of the
fatty acid is less soluble.
Further, the product may be washed such as with water to remove
adventitious impurities therefrom.
The present invention also provides finely divided silver salts of
fatty acids whenever prepared by the process of the present
invention.
In a modification of the process of the present invention,
light-sensitive silver halide grains are added to the colloidal
dispersion of the ammonium or alkali metal salt of the fatty acid
prior to the addition of the water-soluble silver salt so as to
provide a source of catalytic centers for physical development.
A composition prepared in this way can be used in photographic
applications as is described more fully hereinafter with favorable
results. The use of preformed silver halide grains permits
variation and control of the sensitometric properties of the
compositions of the invention, in accordance with the properties of
the grain themselves. Generally, a hydrophilic colloid photographic
emulsion containing the silver halide grains is used and this can
be prepared by well known emulsion techniques. Preferably, a
low-gelatin photographic emulsion is used, i.e., one containing
less than about 30 grams of gelatin per mole of silver halide.
The silver halide grains may be treated, prior to use, in various
ways to modify their properties as is well known in the
photographic art. For example, they may be chemically sensitized.
The silver halide emulsion may contain conventional addenda such as
surfactants to improve dispersion thereof.
The silver halide is preferably added in a concentration of from 3
to 50 mole per cent based on the fatty acid silver salt which is to
be formed.
As mentioned hereinabove, the product of the process of the present
invention is particularly useful in photographic applications. In
particular, it is useful in a radiation sensitive material of the
type comprising a support and containing in a layer or layers
thereof a radiation sensitive compound capable of forming catalytic
centers for physical development on exposure to actinic radiation
such as light, electron radiation, X-rays or gamma-rays, the silver
salt of the fatty acid produced by the process of the invention to
provide a source of silver ions for physical development when
heated to a suitable temperature and a reducing agent. In use,
these materials are given an imagewise radiation exposure to form a
latent image therein and are then processed by heating. Preferably,
they also contain a toning agent to provide a more neutral image
tone. Such photosensitive materials are described, for example, in
U.S. Pat. No. 3,672,904 of DeMauriac, issued June 27, 1972; Belgian
Pat. No. 772,371 issued Oct. 15, 1971 and U.S. Pat. No. 3,152,904
of Sorensen et al, issued Oct. 13, 1964.
An especially useful method of the invention is a method of
preparing a photothermographic composition comprising (a) mixing an
aqueous solution of a water soluble noble metal salt with a
colloidal dispersion comprising a fatty acid reactant comprising
less than 70 mole percent free fatty acid and at least 30 mole
percent ammonium or alkali metal salt of said fatty acid to provide
a reaction mixture, (b) optionally adding an acidic solution to the
reaction mixture to convert any unreacted ammonium or alkali metal
salt to the free fatty acid, (c) recovering the noble metal salt of
the fatty acid and (d) mixing the resulting noble metal salt of the
fatty acid with (i) a photosensitive component, (ii) an organic
reducing agent and (iii) a binder.
The following examples are included for a further understanding of
the invention.
EXAMPLE 1
Behenic acid (10g) was heated with water (100ml) to 85.degree.C. 4M
sodium hydroxide solution (3.7ml) was added slowly to convert 50
mole per cent of the behenic acid to the sodium salt. The mixture
was vigorously stirred. The resulting opalescent suspension was
cooled to 25.degree.C., cold water (60ml) added, and 5M AgNO.sub.3
(2.90ml) added dropwise with stirring to convert the sodium
behenate to silver behenate. The resulting flocculent white
precipitate was filtered at the pump, washed three times with
water, sucked reasonably dry and dried in vacuo over potassium
hydroxide. The product (10.9g) was a loose, free-flowing white
powder, with an average particle size of less than 1.mu.m.
EXAMPLE 2
Behenic acid (10g) was heated with water (50ml) to 85.degree.C. 4M
sodium hydroxide solution (3.7ml) was added slowly with vigorous
stirring to convert 50 mole per cent of the acid to the sodium
salt. The resulting viscous liquid was cooled to room temperature,
and cold water (120ml) added. To this colloidal suspension was
added 5M silver nitrate solution (5.8ml) to which had been added 25
percent ammonia solution (6ml). The ammonia converted a further 40
mole per cent of the original behenic acid to the ammonium salt.
The mixture was stirred gently for four hours, with the addition of
two 1ml aliquots of 25 percent ammonia solution, to replace ammonia
losses. The mixture at this point resembled a thick cream, and 3M
nitric acid (32ml) was added to neutralize excess ammonia. This
caused the mixture to flocculate rendering it easily filterable.
The product was filtered and washed three times with water (250ml
portions) at the pump, and dried. Examination under an optical
microscope showed the particle size to be less than 0.3.mu.m, with
the exception of a few larger particles or aggregates. The silver
ion in the filtrate was estimated gravimetrically by precipitation
with chloride ion, and showed 11 percent of the silver added had
not been converted, corresponding to an 88 percent conversion of
behenic acid to silver behenate.
Examples 3 and 4 illustrate the photographic application of the
products of Examples 1 and 2 respectively.
EXAMPLE 3
In this Example, the silver behenate behenic acid powder prepared
in Example 1 was used in a coating on paper.
The following composition was ball-milled for 90 minutes:
Silver behenate-behenic acid powder prepared in Example 1 3.0 g
polyvinyl butyral (binder) 0.4 g phthalimide (toning agent) 0.34 g
acetone 10 ml toluene 10 ml sodium bromide 0.010 g
Then 0.45g 1,1'-bis-2-naphthol reducing agent dissolved in acetone,
14ml, plus toluene, 5ml was added. The mixture was mixed
thoroughly, coated on paper at a wet thickness of 0.10mm and
dried.
The sodium bromide was added to form a light sensitive silver
bromide by reaction with some of the silver behenate.
Samples of the dried coating were exposed to an Edgerton,
Germeshausen and Grier Mark VII sensitometer for 10.sup..sup.-3
seconds, with no filters, through a bar pattern or a photographic
`step-wedge`. They were processed by contact with a curved aluminum
block heated to 138.degree.C. for about ten seconds. The
bar-pattern-exposed sample showed a good image of black bars on a
white background, with a reflection density difference of 1.2 units
between image and background. The step-wedge exposure showed eleven
0.15 density increment steps. The coatings were smooth and of good
quality.
EXAMPLE 4
This example illustrates the use of the product of Example 2 in the
preparation of film coatings. The following composition was
ball-milled for one hour:
silver behenate/behenic acid composition 1.75 g From Example 2 30%
polyvinyl butyral (binder) in 1:1 acetone/toluene 20 ml phthalimide
(toning agent) 0.17 g sodium bromide (to provide light sensitive
silver bromide) 0.05 g
Then the following solution was added:
1,1'-bis-2-naphthol (reducing agent) 0.22 g polyvinyl butyral
(binder) 1.00 g acetone 14 ml toluene 5 ml and the mixture
ball-milled a further five minutes. It was coated on a polyethylene
terephthalate support at a wet thickness of 0.1 mm, allowed to dry
and overcoated with a 6.6 percent solution of polyvinyl butyral in
2:1 acetone/toluene, at a wet thickness of 0.1 mm which was also
allowed to dry.
A sample was exposed through a negative to a small electronic
flash-gun nine inches distant for about 10.sup..sup.-3 seconds. The
exposed material was heat-processed for 10 seconds at 138.degree.C.
as in Example 3. A brown-black image, optical density 0.90 with a
background density of 0.05 was obtained.
EXAMPLE 5
This example illustrates the preparation of lightsensitive silver
behenate/silver bromide/behenic acid compositions in accordance
with the modification of the process of the invention described
above. The silver bromide grains used were in the form of a
coagulum cubic silver bromide grains of edge-length 0.31 microns
and were prepared by conventional double-jet techniques in the
presence of 25g of phthalated gelatin per mole of silver bromide,
and the pH of the resultant emulsion then lowered so as to
precipitate the silver bromide and gelatin together as a coagulum.
The aqueous phase was then substantially removed.
Behenic acid (10g) was heated with water (50ml) to 82.degree.C. and
4M sodium hydroxide solution (3.7ml) was then added slowly with
vigorous stirring. To the resulting milky-opalescent suspension was
added cold water (150ml). This diluted suspension was strained
through muslin and brought to 40.degree.C.
Under safelight conditions, some coagulum as described above,
containing about 0.15g of silver bromide, was dispersed in water
(50ml), to which a drop or two of sodium hydroxide solution had
been added to bring the pH to about 8, at 40.degree.C. This
dispersion was added to the behenic acid/sodium behenate
suspension, and the combined suspension stirred vigorously for 5
minutes. 5M silver nitrate solution (2.9ml), diluted with 10ml of
water, was then run in slowly with vigorous stirring, and the
mixture stirred thoroughly for 10 minutes at 40.degree.C. It was
cooled to room temperature and stood in the dark for ninety
minutes. Then the mixture was filtered, the precipitate washed
three times with water and dried in vacuo over potassium hydroxide.
The result was a fine white powder, yield 10g. Example 6
illustrates the photographic application of the product of Example
5.
EXAMPLE 6
The following composition was ball-milled in the dark for seventeen
hours, using 5mm diameter glass balls:
silver behenate/silver bromide/ behenic acid powder prepared in
Example 5 1.5 g phthalimide (toning agent) 0.16 g polyvinyl
butyral, (binder) 3% w/v solution in 50-50 acetone-toluene 10
ml
Then the following mixture was added and the combined mixture
ball-milled a further ten minutes:
1,1'-bis-2-naphthol (reducing agent) 0.20 g polyvinyl butyral
(binder) 0.50 g acetone 8 ml toluene 3 ml
The dispersion was coated on paper at a wet thickness of 0.10 mm
(0.004 inches), and the coating dried.
The resulting material was divided into two portions. One portion
was given a saturation exposure through a bar-pattern to an
electronic flash gun 12 inches distant and the other portion was
exposed through a step tablet having 0.15 density increment steps
to an Edgerton, Germeshausen and Grier Mark VII Sensitometer for
10.sup..sup.-3 seconds with no filters. The exposed portions were
processed by heating on an aluminum block at 128.degree.C. until
background density started to form. Densities were read by a
diffuse reflection densitometer and the results are given in Table
I below. Examples 7 and 8 illustrate the photographic applications
of compositions prepared as in Example 1.
EXAMPLE 7
A coating was prepared as in Example 6, except that a silver
behenate/behenic acid powder prepared as in Example 1 was used in
place of the powder prepared in Example 5. Further, 1 percent
lithium bromide solution in acetone (0.5 ml) was added to the
composition before being milled for seventeen hours. The resulting
material was tested in the same way as the material of Example 6.
The results are shown in Table I below.
EXAMPLE 8
A coating was prepared as in Example 7, except that some coagulum
as described in Example 5 (0.02 g AgBr) was washed thoroughly with
acetone and added in place of the lithium bromide solution. The
resulting material was tested in the same way as the material of
Example 6. The results are shown in Table I below.
Table I ______________________________________ Saturation
Speed-Step No. at Stated Exposure Density above D.sub.min Example
D.sub.max D.sub.min 0.05 0.1 0.2 0.5
______________________________________ 6 1.57 0.17 21 201/2 20-11 9
7 1.50 0.17 9 81/2 71/2 61/2 8 1.10 0.34 7 5 3 --
______________________________________
The speeds are quoted as the step-number (densest step in the table
21) which give the stated density above fog. The material of
Example 7 was of high contrast, while that of Example 6 was of
moderate contrast but having a very long `toe` of low, uniform
density. The material of Example 8 showed lower density, contrast
and speed. It will be noticed that the material of Example 6 shows
comparable image density and substantially greater photographic
speed compared with the material of Example 7.
The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *