Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~037761
My invention relates to phosphine sensitized silver
halide emulsions which can be further sensitized with chemical
sensitizers and to photographic elements including such
emulsions.
The use of phosphorus and its compounds as sensitizers
for photographic silver halide emulsions and elements is kno~n
in the art. For example, British Patent 1,057,949, published
February 18, 1967, teaches the sensitization of silver bromide
emulsions by developing in the presence of an amido-phosphoric
acid polyethylene glycol ester. British Patent 1,295,463,
published November 8, 1972, teaches that silver halide emulsions
can be sensitized through the use of gelatin which has been
treated with phosphine or white phosphorus. Thurston U.S.
Patent 3,338,712, issued August 29, 1967, teaches sensitizing
emulsions containing labile sulfur compounds by the incorpora-
tion of organic phosphites. Carroll et al U.S. Patent
2,271,622, issued February 3, 1942, teaches the sensitization
of silver halide emulsions using cationic surface-active
phosphonium salts. Lowe et al U.S. Patent 3,523,023, issued
20 August 4, 1970, teaches the sensitization of silver halide
e~ulsions with hydroxyalkyl phosphonium salts. Willems et al
U S. Patent 3,552,968, issued January 5, 1971, teaches
sensitization with phosphonitrile trimer and tetramer
derivatives. Russian Patent 195,872, published July 11, 1967, :
discloses to be sensitizers for silver halide emulsions
triphenyl phosphines, including those having alkyl, aryl,
alkoxy or dialkylamino phenyl substituents.
While varied phosphorus containing compounds have
been recognized to be sensitizers for photographic silver
30 halide emulsio~s, it should not be assumed that phosphorus
compounds are, in general, useful as silver halide sensitizersr
Phosphorus compounds, in fact, cover the full gamut of
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' ' ' ,. '
~037761
performance characteristics, ranging from densensitizers to
sensitizers. Even among those classes of phosphorus compounds
known to be sensitizers unexplained variations in performance
are observable. One difficulty with many phosphorus sensitizers
has been their ineffectiveness and/or incompatibility with other
chemical sensitizers. For example, some phosphorus sensitizers
in combination with heavy metal sensitizers, such as gold
sensitizers, produce no additional speed increase while others
produce prohibitively large increases in fog.
I have discovered quite unexpectedly a class of
phosphine compounds to be useful as sensitizers for silver
halide emulsions. More surprisingly I have found these compounds
to be capable of producing additional increases in photographic
speed when employed in combination with conventional chemical
sensitizers. Still further, silver halide emulsions containing
these compounds as sensitizers either alone or in combination ~ -
with other chemical sensitizers show surprisingly low fog
levels. By contrast, I have observed distinctly inferior
comparative performance for certain closely related and
homologous phosphine compounds.
In one aspect then, m~ invention is directed to a photo-
graphic silver halide emulsion comprised of silver halide grains,
a vehicle for dispersing said grains and a sensitizing amoun~ of-
a tris(dialkylamino)phosphine or a tris(dialkylaminoalkylene)phosphine in which each of the alkyl groups contains at least two
carbon atoms and each alkylene group contains from one to three
carbon atoms. In another aspect, my invention iS directed to a
photographic element incorporating such a photographic emulsion.
My invention may be better understood and appreciated
by reference to the following detailed description:
. . . _ . _ c . _
1037~
The phosphine compounds which I employ in the
practice of my invention are those having three dialkylamino
groups attached directly to the phosphorus atom or through
an intervening methylene linkage of up to three carbon atoms.
The alkyl groups can be independently chosen, but in each
instance include at least two carbon atoms.
Preferred phosphine compounds of this type are those
represented by the following structural formula:
f 10 ~ (CH2)n3--p ~ ~
R' 3
wherein, R and R' are alkyl groups having from 2 to 8 carbon
atoms, preferably 2 to 5 carbon atoms, and n is an integer of
from 0 to 3 inclusive.
Exemplary preferred phosphine compounds useful in the
practice of this invention are set forth in Table I. The first
two phosphine compounds listed in Table I, though closely
structurally related to those that follow, form no part of
my invention, but are included solely for purposes of
comparison.
TABLE I
- PS~
~3 ~ ' .
triphenyl phosphine
,
. ,
... ., __ . _ . _
1.()37761
PS-2
~ N /
C ~ ¦ CH
N - P-N\
C~3 CH2
tris(dimethylamino)phosphine
'.:
; PS-3
. . .
C 2H~ /C 2H 5
.;~ N
C2~ / 2 5
: / N - P-N \
C2H5 2 5
:tris(diethylamino)phosphine
. .
Ps-4
- i_C3H~ _-C3H7
N
l_C3~ ~ _-C3H7
- N- P-N \
-C3H7 _ 3 7
tris(di-i-propylamino)phosphine
: PS-~
",n-C4Hg n~C4H9
\ N
n-Cl~Hg I n-C4Hg
- / N- P-N \
: n-C4Hg n C4Hg
tris(di-n-butylamino)phosphine
: 5
, _ =
- PS-6 1~37~
, ~ n-C6~ ~C6H~
- n-C6~ ~ 6 11
N- P-N \ :,
n-C6H1 n C6H11
tris(di-n-hexylamino)phosphine
'
~ PS-7
,, C 2H~ ~C 2H 5 ' '
IN '.:'
.. CH ~;
: C2H ~ ¦ /C2H5
/ 2 P CH2 N
C H 2 5 ,:-~
tris(diethylaminomethylene)phosphine
PS-8
:- 2 ~ / 2 5
7 ~-:
., (CH2)2 '~
2 ~ ¦ / 2 5
( 2)2 ( 2)2
: 2 5 C2H5
tris(diethyl minodimethylene)phosphine
.'. ~ ~,,.~.,.
. .
,' ~
.
- . ~ .
PS-9 ~ 37761
N
(fH3)3
2H5 ¦ / 2 5
/ N-(cH3)3-p-(cH3)3-N\
- C H 2 5
tris(diethylaminotrimethylene)phosphine :~
. ~ '
PS-10
n-C4H~ n-C4Hg
Nl
CH2
~ n~C4H~ ¦ n-C4Hg
. n-C4Hg n~C4H9
tris(di-n-butylaminomethylene)phosphine
..,,~ '
: ~ PS-
. n-C ~ ~ C8H17
.. ~ N
CH2
':' ,:
n-C8~ n-C8H17
N CH2 P CH2 N \
n-C8H17 n-C8H17
- tris(di-n-octylaminomethylene)phosphine
'~
-7-
: ` :
~}37761 ~ -
The preparation of compounds of this type is
generally well known in the art. For example, an
exemplarly technique suitable for preparing these
compounds is disclosed by Carl Stauebe and Herman P.
Lankelma in J. Am. Chem. Soc., Volume 78, pages 976
through 977 (1956), in an article entitled "Hexaalkyl
Phosphorus, Phosphoric and Phosphoricthioic Triamides."
` The silver halide e~lulsions used in accordance with the
sensitizers of my invention can comprise, for example, silver
chloride, silver bromlde, silver bromoiodide, silver chloro-
bromide, silver chloroiodide, silver chlorobromoiodide and
mixtures thereof. The emulsions can be coarse or fine grain
emulsions prepared by any of the well-known techniques, e.g.,
single Jet emulsio!ls, such as those described in Trivelli and
-
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. .
.
: , - . . ~ . ,
'' ~037q~1
Smith, ':L`he PhOtOé~1`ar)II iC JOUI na1~ VO1 . LXX1X, 1V1aY, 1939 (PP 330-
338); double Jet emulsions, such as those described in Glafkides,
I'noto-~ral~hic Chemistry, Vol. 1, Chapter 28, Fountain Press,
London, 1958; arnmoniacal, thiocyanate or thioether ripened
. .
; emulsions SUCh as those described in Nietz et al U.S. Patent
2,222,264, issued November 19, 1940; Illingsworth U.S. Patent
3,320,o69, issued May 16, 1967 and Jones U.S. Patent 3,574,628,
issued April 13, 1971.
The silver halide emulsions utilized in -this invention
can be surface sensitized anl/or internally sensitized. One
convenient approach for forming internally sensitized emu].sions
is to sensitize the grain surfaces of an emulsion to be employed
as a core emulsion lollowed by the further deposition of silver
halide on the sensitized surfaces of the grains. E~emplary of
internal image forming silver halide enulsions which can be used
in the practice of this invention with phosphine sensitizers
are those sensitized predominantly on the interior o~ the silver
,! halide grains as described in Porter et al U.S. Patent 3,206,313,
issued September 14, 1965; Porter et al U.S. Pa~ent 3,317,322,
20 issued ~lay 2, 1967; Spence et al U.S. Patent 3,690,891, issued
Septernber 12, 1972; and ~vans U.S. Patent 3,761,276, issued
- Septenber 25, 1973.
The silver halide ernulsions can be regular grain
emulsions such as the type described in Klein and Moisar, J.
Phot. Sci., Vol. 12, No. 5, Sept./Oct., 1964, pp 242-251 and
German Patent 2,107,118. Negative type emulsions can be utilized,
as well as direct-positive emulsions as described in Illingsworth
U.S. Patent 3,501,307, issued ~larch 17, 1970 and Berriman U.S.
Patcnt 3,367,773, issued l;ebruary 6, 1968; such emulsions being
surface fog~ed in addition to being internally sensitized.
:: :
lQ377~1
.. , . ~:
Inasmuch as the phosphine sensitizers of my inven-
tion produce further enhanced photo~raphic speeds when employed
in combillation with ~nown chemical sensitizers, silver halide
emulsions employed in the practice of my invention are pre-
ferably chemically sensitized according to conventional practice
in addition to including the phosphine sensitizers. My silver
halide emulsions can be usefully sensitized with chemical
sensitizers, such as with sulfur, selenium or tellurium compounds;
gold, platinum or palladium compounds; or combinations of these.
Procedures for chemically sensitizing silver halide emulsions are
described in Sheppard et al U.S. Patent 1~623~499~ issued April 15,
j 1927; Waller et al U.S. Patent 2~399~083~ issued April 23~ 1946
~ McVeigh U.S. Patent 3~297~44~ issued January 10, 1967~ and
-~ Dunn U.S. Patent 3~297~446~ issued January 10, 196rf.
~ ly phosphine sensitizers can be added in a variety
of ways to photographic emulsions and at various stages in the
preparation thereof; however, I prefer to introduce the phosphine
.:..
sensitizers of my invention immediately~after chemical sensitiza-
tion by conventional techniques has been completed and before
3 20 other addenda have been incorporated into the emulsion. The
sensitizers can be added with useful effects at tihe completion
of Ostwald ripening and prior to one or more of the final
. .~. .
digestion operations. The sensitizers are preferably added to
the silver halide emulsion after the silver halide grains are
substantially in their final size and shape. Thephosphine
sensitizers can be added in methanol, acetone or other innocuous
organic solvents. To avoid thermall~ degrading the phosphine -
sensitizers it is eenerally preferred that the silver halide
!
::
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.... ~ . . .
.
~i ~
emulsion not be maintain~ above a temperature o~ about 50 to
; 60C for an e;~tended period in preparation steps su~sequent to
phosphine incorporation. ~ffective phosphine sensitization
can be obtained by holdin~ tne emulsion at an elevated tempera-
ture of up to about 40C or more for a period ranging from a
few minutes to an hour or more--preferably 10 to 40 minu~es.
Any sensitizing amount of the phosphine compounds of
this invention can be usefully incorporated into the silver
I halide emulsion. Typically concentrations of from about 0.1
; 10 to 100 mg of phosphine sensitizer per mole of silver halide,
preferably 0.5 to 50 mg of phosphine sensitizer per mole of
silver halide, can be employed.
Since higher concentrations of the phosphine sensitizers
can raise fo~ levels, the maximum concentrations of the phos- -
phine sensitizers is a function of (a) the amount of background
.'
fog compatible with the particular photographic application
and (b) whether or not an antifoggant is incorporated in the
silver halide emulsion. While the phosphine sensitizers are
; . generally compatible with known-antifo~gants and stabilizers,
I have found tne phosphine sensitizers employed in the practice
of this invention to be particularly effective in combination
with known azaindene antifo~gants, most preferably tetrazaindene
antifoggants. Exemplary antifoggants and stabilizers, each used
¦ alone or in combination include the followin~:
a) thiazolium salts described in Brooker et al U.S.
Patent 2,131,038, issued September 27, 1938 and Allen et al U.S.
Patent 2,694,716, issued November 16, 1954;
b) the a~aindenes described in Piper U.S. Patent
i 2,886,437, issued riay 12, 1559 and ~eimbach et al U.S. Patent
30 2,444,605, issued July 6, 1948;
'. ! ` .
- ; ~
:: .
!
c) the mcrcur ~sa~s as described in Allen et al U.S.
.. . .
Patent 2,72~,663, issued December 27, 1955;
~ ~ d) the urazoles described in Anderson et al U~S. Patent
~ 3,287?135, issued Nrovember 22, 1966;
~ e) the sulfocatechols described in ~ennard et al U.S.
i ~atent 3,236~652, issued February 22, 1966;
f) the oY~imes descri~ed in Carroll et al British Patent
623,448, issued May 18, 1949;
g) nitron;
h) nitroindazoles;
1 i) mercaptotetrazoles described in Kendall et al U.S.
; Patent 2,403a927, issued July 16, 1946; Kennard et al U.S. Patent
.; 3,266,897, issued August 16, 1966; and Luckey et al U.S. Patent - ;
::: 3,397,987, issued ~ugust 20, 1968;
j) the polyvalent metal salts described in Jones U.S.
Patent 2,839,405, issued June 17, 1958;
k) the tlliuronium salts described in Herz et al U.S.
, .
Patent 3,220,~39, issued November 30, 1965; and
1) the palladium, platinum and gold salts described in
. 20 Trivelli et al U.S. Patent 2,566,263, issued August 28, 1951; and
t Yutzy et al U.S. Patent 2,597,915, issued May 27, 1952.
. In addition to the components above mentioned the
silver halide emulsions include a vehicle for dispersing the
silver halide grains. The vehicle is typically a hydrophilic
l colloid, such as gelatin, but can take any conventional form.
I In addition, the silver halide emulsion can contain any one or a
! variety of conventional photographic emulsion addenda, such as
hardeners, spectral sensitizers, brighteners, COatLng aids,
plasticizers and lubricants, absorbing and filter dyes, develop-
ing agents, developlnent modifiers, etc. Typical conventional
vehicles and addenda of this type useful in the practice of this -~
-12-
. , '.
. q
- . : : ..
`
invention are disclose~ ln Product Licencing Indcx, Vol. 92
December 1971, publication 9232, pages 107 through 110.
~ .
The photographic emulsions according to my invention
can be employed as coatings in single and multi-layer photographic
elements. Such elements typically include a conventional photo-
graphic support of the type disclosed specifically in paragraph
X of Product Licensing Index, cited above. The photographic
emulsion layers can be employed in combination with subbing,
interlayers, Carey Lea silver layers, antihalation layers, etc.,
as is well understood in the art.
The photographic elements according to my invention
; can be applied to a variety of applications. The photographic
elements can be used with X-rays or can be orthochromatic, pan-
chromatic or infrared sensitive. The photographic elements can
be employed to forrn black-and-white images or to form colored or
multi-colored images in one or a plurality of layers as taught
specifically in paragraph XXII of Product Licensing Index, cited
above. The photographic elements can be of a type which form
images upon development in conventional silver halide developing
solutions, which form images by dry physical development, which
form images by image transfer, etc. The photographic elements
can be employed as lithographic printing plates as taught in
paragraph XXIV of Product Licensing Index, cited above. The
photographic elements can be formed to produce positive or nega-
tive images and can be formed to be of the direct print type, as
specifically disclosed in paragr~ph-XXV of Product Licensing-
Incle~, cited above.
-~ The following examples are intended to further illus-
trate my invention.
-13-
10377ti~ ~
Examples 1 through 10
A silver bromide emulsion having a mean grain size of
0.4 micron in diameter was prepared using a conventional double
jet technique. 'rhe emulsion was separated into equal portions
and chemically sensitized to a maximum obtainable speed using
none, one, or a combination of the sul~ur sensitizer sodium
thiosulfate and/or the gold sensitizer potassium chloraurate,
as shown below in Table II. The emulsion samples were finished
as shown in Table II, and the phosphine compound was then added
as a coating addenda at the concentration shown in Table II.
The phosphine sensitizer was added at 40C and the emulsion
sample was held at this temperature for 20 minutes. The
-~ emulsion samples were then coated on a film support at 20 mg
silver per square decimeter, exposed, developed for 4 minutes
in Kodak Developer D-l9 (the composition of which is set forth
at page 43 of Kodak Advanced Data Book J-l, titled Processing
Chemicals and Formulas for Black-and-White Photography, 6th ~ -
edition, published 1963), fixed, washed and dried.
In comparing Example 1 with Control 1 it is apparent
that the phosphine sensitizer more than doubled the speed of the
emulsion. In comparing Examples 2 and 3 with Controls 2 and 3
it is apparent that the phosphine sensitizer in combination
with the sulfur sensitizer produced an emulsion more than 3 times
faster than the emulsion containing the sulfur sensitizer alone.
Comparing Examples 4, 5 and 6 with Controls 4, 5 and 6, adding
the phosphine sensitizer to the sulfur and gold sensitized
emulsion produced a greater than two-fold speed increase.
Finishing the sulfur and gold sensitized emulsions improved
speed, but was not essential to achieving further speed increases
with the phosphine sensitizers. The phosphine sensitizer
PS-3 increased fog by 0.01 or less in all instances, even when
-14-
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employed in combination Wl~g the gold sensitizer. While the
phosphine sensitizer PS-7 in combination with the sulfur and ;~ -
gold sensitizer increased fog, this was by less than 0.20 and
therefore clearly acceptable for many photographic applications.
Examples 11 through 26
A silver bromoiodide emulsion containing 6 mole percent
iodide was chemically sensitized to a maximum attainable speed
using 12.0 mg o~ sodium thiosulfate and 4.4 mg of potassium
chloraurate per silver mole. The emulsion was separated into
equal portions, and the samples forming the examples were further
sensitized with the phosphine compounds as set forth in Table III.
The emulsion samples at the time of adding the phosphine compounds
were stirred at 55C, then lowered to 40C. Spectral sensi-
tizers were added to certain of the samples as indicated in
Table III followed by holding for 10 minutes at 40C. An anti-
foggant, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, was then ~ -
added to certain of the emulsion samples, as indicated in Table
III. The emulsion samples were coated as in Example 1. A por-
tion of each film coating was exposed on an Eastman lB sensi-
tometer through a continuous step wedge and through either a
Wratten 35 + 38A (Blue) filter or a Wratten 16 (Minus Blue)
filter and processed as in Example 1. The results, su~marized
in Table III, show that both the blue and minus blue speeds of
the spectrally sensitized silver halide emulsions are enhanced
by the phosphine sensitzers of this invention used in combination
with sulfur and gold sensitizers. Fog levels are not prohibitively
high without the antifoggant being present, but are reduced to
very low levels through the incorporation of the antifoggant.
-16-
... . .
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tCH2)3 C2H5 (1~ C1
53 SO3
Anhydro-5,5~-dichloro-9-ethyl-3,3~-bis- .
: (3-sulfopropyl) oxacarbocyanine hydroxide,
- triethylamine salt ~
.' :
.,` .
': ' , '`'~
--
' , - . .~ .
.,' ''
....
. : . . : ` . - : . . ~ . .
:
: ~037q~1 ~
Dye D
,
, :' ' C2H5 . C2H
\~ ~S~ - N I /o~ /Cl
~cn--c H = c~--o ~g 11 1 ~
Cl/ ~ \ ~5 \ Cl
C2H5 ICsl2 2
Cll--CH ~ : -
' S o'9
Anhydro-5,5',6,6'-tetrachloro-1,1'-3-triethyl-
3'(3-sulfobutyl) benzimidazolocarbocyanine
hydroxide
Exam~les 27 and 28
; A silver bromoiodide emulsion containing 6 mole
percent iodide was chemically sensitized to a maximum
attainable speed using 12.0 mg of sodium thiosulfate and 4.4
~ 10 mg of potassium chloroaurate per mole of silver. The emulsion
was separated into equal portions, and phosphine compounds as
set forth in Table IV were added to separate portions. The
- emulsion portions were at 55C at the time the phosphine
compound was added and were-then reduced in temperature to
40C and held for 20 minutes. The results are summarized below
in Table IV.
,: - .
'' '
. .
' ~'
' ' :
-20- . - ~
. .
- . . . . .
, . : . ,
~(~377~
Table IV
- Concen~ra- Relative
Example Phosphine tion (mg/ Blue
No. Compound Ag mole) Speed Gamma Fog
Control
17 None None 100 1.5 o . o8
Compara-
tive
Example PS-l 13.2 100 1.5 0.07
Compara-
tive
Example PS-2 3.0 105 1.5 o.o6
Compara-
tive
Example PS-2 30.0 94 1.6 0.05
: 27 PS-3 3- 182 1.3 0.10
28 p~_3 6.o 246 1. 5 o . 13
''',
In comparing Control 17 with the Comparative Examples
employing triphenyl phosphine ànd tris(dimethylamino)phosphine,
it is apparent that the properties of the emulsions are only
.
marginally modified, if at all, by the incorporation of these
phosphine compounds. On the other hand, when the phosphine
sensitizer of this invention, tris(diethylamino)phosphine, is
incorporated in the emulsion a very significant increase in the
~elative blue speed is apparent. This result could not be
predicted from the comparative examples. - `
In addition to the phosphorus containing sensitizers
disclosed herein, I have also discovered phosphorus imides of
adamantane structure to be useful chemical sensitizers. -
The invention has been described with particular
reference to preferred embodiment-s there~f-but-it will;-be under--
stood that variations and modifications can be effected within
the spirit and scope of the invention.
-21-
, -~
